Volume 51

Number 4
21 February 2022
Pages 1199–1550

Chem Soc Rev

Chemical Society Reviews
rsc.li/chem-soc-rev

ISSN 0306-0012

REVIEW ARTICLE
Corrado Di Natale et al.
Corroles at work: a small macrocycle for great applications
 Chem Soc Rev
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REVIEW ARTICLE View Journal | View Issue

Corroles at work: a small macrocycle for

great applications
Cite this: Chem. Soc. Rev., 2022,
51, 1277 a b c
Corrado Di Natale, Claude P. Gros and Roberto Paolesse

Received 9th July 2021
DOI: 10.1039/d1cs00662b
rsc.li/chem-soc-rev
Corrole chemistry has witnessed an impressive boost in studies in the last 20 years, thanks to the possibility
of preparing corrole derivatives by simple synthetic procedures. The investigation of a large number of
corroles has highlighted some peculiar characteristics of these macrocycles, having features different from
those of the parent porphyrins. With this progress in the elucidation of corrole properties, attention has
been focused on the potential for the exploitation of corrole derivatives in different important application
fields. In some areas, the potential of corroles has been studied in certain detail, for example, the use of
corrole metal complexes as electrocatalysts for energy conversion. In some other areas, the field is still in
its infancy, such as in the exploitation of corroles in solar cells. Herein, we report an overview of the
different applications of corroles, focusing on the studies reported in the last five years.

1. Introduction
a
Department of Electronic Engineering, University of Rome Tor Vergata, Viale del
Politecnico, 00133 Rome, Italy. E-mail: dinatale@uniroma2.it; In the large family of porphyrin analogs, i.e. pyrrolic macro-
Tel: +39 06 72 59 73 48 cycles with skeletal variations in the parent porphyrin, corrole
b
Université Bourgogne Franche-Comté, ICMUB (UMR CNRS 6302), (Fig. 1) has recently assumed a protagonist role. This con-
9 Avenue Alain Savary, BP 47870, 21078 Dijon, Cedex, France.
tracted macrocycle is not a new member because it was
E-mail: Claude.Gros@u-bourgogne.fr; Tel: +33 03 80 39 61 12
c
Department of Chemical Science and Technologies, University of Rome Tor
reported for the first time in the early 1960s, during the attempt
Vergata, Via della Ricerca Scientifica 1, 00133 Rome, Italy. to find a synthetic route for the preparation of Vitamin B12 by
E-mail: roberto.paolesse@uniroma2.it; Tel: +39 06 72 59 47 52 Johnson and Kay.1

Prof. Corrado Di Natale. Received Prof. Claude P. Gros. Graduation

a Laurea in Physics from the
University of Rome La Sapienza
in 1987. Since 1991, he has been
with the University of Rome Tor
Vergata where he is full professor
of Electronics. His studies have
been carried out in the field of
chemical sensors, most of his
contributions were in the
development of porphyrinoids
based electronic noses and
Corrado Di Natale electronic tongues and their
applications to different fields
such as food analysis, environmental control, and medical
diagnosis. Among the various applications, he pioneered in 2003
the diagnosis of lung cancer with gas sensors. He has published
more than 340 papers in refereed journal and several book
chapters. His papers have been cited more than 12500 times and
his h-index is 61 (source Scopus). He is co-inventor of eight patents
and contributed to fund two spin-off companies.
in Chemistry from the Université
de Bourgogne in 1995 under the
supervision of Prof. R. Guilard.
After a one-year post-doc
position in California (UCDavis)
in the lab of Prof. K. M. Smith
working on chlorins and
pyrroloporphyrins, he started his
career as an Assistant Professor
at the Université de Bourgogne,
where he has been Full Professor
Claude P. Gros of Organic Chemistry since 2009
(at the medicinal/pharmaceutical
school). His research interests include the synthesis and reactivity
of corroles, porphyrins, BODIPYs and dipyrrins and their metal
complexes with applications in energy and electron transfers, gas
sensors and medicinal chemistry. He is the co-author of 155 papers
in international journals (H-index 40; 44350 citations), and he is
the coinventor of four patents.

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Fig. 1 The molecular structure of corrole.
For several years, the pathways necessary to synthesize
corroles2 have limited the detailed studies of its properties,
until the definition of a simple route for the preparation of
triarylcorroles from synthetic precursors3,4 boosted studies on
the characterization and consequently on the application of
corrole derivatives.
From the beginning, this macrocycle has revealed peculiar
and frequently difficult to interpret behavior, which has led to
several incorrect characterizations of some corrole complexes,
and even the first corrole report in the literature was later
amended by Johnson.5 The somewhat unpredictable behavior
of corrole can be related to its structural characteristics: the
contracted macrocycle imparts three pyrrolic hydrogens in the
core, which leads to a non-planar structure for the free-base
corrole.6 This feature causes the higher acidity of corrole than
porphyrin.7 The trianionic character as a ligand makes corrole
a strong s-donor, able to stabilize coordinated metals in
formally high oxidation states; however, the high electron
density and high oxidation state of the metal also makes the
ligand-to-metal charge transfer facile, with the formation of the
corrole p–cation radical, leading to the non-innocence of
Prof. Roberto Paolesse received a
Laurea degree in Chemistry
(Summa cum Laude) from the
University of Rome La Sapienza
in 1983. After a post-doc period at
the same University, he has been
at the University of Rome Tor
Vergata since 1986, and he is
now full professor in Chemistry
at the Department of Chemical
Science and Technologies. His
research interests cover the
Roberto Paolesse synthesis and characterization of
porphyrinoids and their appli-
cations in chemical sensors, sensors arrays and optoelectronic
devices. He serves as Associated editor of the Journal of
Porphyrins and Phthalocyanines since 2006. He is author and
co-author of more than 430 research articles (H-index 57-June
2021), and edited two books.
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Chem Soc Rev
corrole as a ligand.8 Corroles also possess strong emissions,
with quantum yields usually significantly higher than porphyrins,
making them of interest as efficient fluorophores.
All these features make corrole chemistry significantly dif-
ferent from that of the corresponding porphyrin and conse-
quently interesting from the applications of these species in
different exploitation fields, ranging from catalysis to sensing
or clinical applications.
These aspects have been reviewed in the past9 so in this
review we describe the most recent exploitations of corrole
derivatives, to give an update on the different uses of corroles in
different application fields. For this reason, this review has
been divided into different sections, according to the various
examples of corrole exploitation.
2. Catalysis
2.1 Oxidation
The exploitation of corroles as catalysts has been one of the first
attempted applications of these derivatives.10 The peculiar
behavior of corrole, which makes this macrocycle different
from the parent porphyrin analogs while retaining some simi-
larities, has been of interest to mimic the chemistry of the
tetrapyrrole biological systems.11 Following the research wave
on the oxidation of hydrocarbons catalysed by synthetic metal-
loporphyrins, the first examples of corrole applications were
related to their use as oxidation catalysts. The interest was
mainly due to the initial assumption that corrole should
stabilize the higher oxidation states of coordinated metals, as
intriguing mimics of biologically active species, and this feature
has been the springboard for the first corrole application as
oxidation catalysts soon after the reports of the synthetic routes
to triarylcorroles, in particular TPFCorrH3.
This topic has facilitated an impressive boost in corrole-
related papers in the first decade after the year 2000 and the
results obtained have been reviewed in the past.12–18 In more
recent years, the finding that the high oxidation states of corrole-
coordinated metals are frequently only formal,19 due to the easy
oxidation of the corrole ligand to the corresponding radical
cation, and the more complex and intriguing coordination
chemistry of corrole opened the applications to a wider range
of reactions than hydrocarbon oxidation. However, further exam-
ples of metallocorrole-catalysed hydrocarbon oxidations have
been reported in the literature, focusing the investigations on
Fe and Mn derivatives.
TPFCorrFeCl has been used to catalyze the hydroxylation of
cyclohexane and adamantane with m-chloroperbenzoic acid as the
oxygen donor.20 In both cases, the reaction was highly selective in
affording the corresponding alcohols, with no traces of ketones;
high regioselectivity was also observed in the case of adamantane.
The same group also studied hydrocarbon oxidation using
hydroperoxides and T(2,6-F2)PCorrFeCl as the catalyst.21 In this
case, different substrates, such as alkanes, alkenes, alkylben-
zenes, and alcohols have been oxidized and the mechanism of
the reaction evidenced the role of the iron corrole complex in
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Chem Soc Rev
activating the hydroperoxide, generating the corresponding
oxygenated radical.
In subsequent investigations, the same group tested analogous
Mn corrole complexes, TPFCorrMn, T(2,6-F2)PCorrMn, and the
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eight-brominated Br8TPFCorrMn, as catalysts for the same
reactions.22,23 In the case of the adamantane oxidation, a
preference for the formation of the tertiary alcohol was again
observed, with the three complexes showing a similar catalytic
activity.22 The catalytic system was also tested for the oxidation
of cyclohexane and alkylbenzenes, affording moderate yields of
the corresponding ketones and alcohols, with the fully bromi-
nated Mn derivative being the most efficient system. Spectro-
scopic investigations have supported the formation of the
CorrMnVO, which was confirmed by following the kinetics of
the reaction with 2,4,6-tris(tert-butyl)phenol. In this case, the
formation of the stable phenoxyl radical via H-atom transfer
could easily be identified by UV-vis spectroscopy, giving infor-
mation on the possible catalytic cycle, which involves the
formation of a CorrMnIVOH species, as observed in the case of
the analogous complex of corrolazine.24
The three Mn corrole complexes were also tested in the
alcohol oxidations with tert-butyl hydroperoxide as the oxidant.
The corresponding aldehydes and ketones were obtained as
reaction products, with no observation of over-oxidation spe-
cies such as carboxylic acids. The perbrominated complex in
this case was also the most efficient system although, in all
cases, the complete bleaching of the catalyst was observed at
the end of the reaction.
Zhang and coworkers reported the olefin oxidation catalysed
by TPFCorrFeIII(OEt2)2 with iodobenzene diacetate as a reagent.25
This mild oxidant showed the advantage to avoid corrole
bleaching, which is one of the major drawbacks in the exploitation
of corrole complexes in these reactions. The catalytic activity, the
product selectivity, and the stereo-retention observed in the
catalytic epoxidation of cis-cyclooctene were among the major
improvements obtained using iodobenzene diacetate. A cataly-
tic cycle involving the formation of a CorrFeVO as the active
oxidant species was proposed (Fig. 2).
The same catalytic system was tested for the oxidation of
sulfides.26 In this case, two catalysts, TPFCorrFeIII(OEt2)2 and
TPCorrFeIII(OEt2)2, were tested, again using iodobenzene dia-
cetate as a mild oxidant. This choice allowed the use of the
more electron-rich TPCorrFeIII(OEt2)2, which usually suffers
from bleaching in the oxidation reactions. This complex
showed higher catalytic activity than the perfluorinated analog,
with 100% conversion of thioanisole within 1 h, with the
Fig. 2 Catalytic cycle for cyclooctene oxidation catalysed by CorrFe.25
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Fig. 3 The catalytic cycle for sulfide oxidation catalysed by CorrFe.26
necessary addition of a few mL of water. The reaction was also
selective toward the formation of sulfoxide, without the over-
oxidation to the corresponding sulfone. Other oxidants than
iodobenzene diacetate gave worse results, also inducing the
catalyst bleaching. In this case, a putative CorrFeVO species was
also proposed as an active oxidant species but a different fate
was evidenced for the transient species, which relaxed to the
corresponding (Corr+ )FeIVO in the case of TPCorr, while it
underwent comproportionation in the case of TPFCorr to give
the corresponding m-oxo complex (Fig. 3).
The same group later studied the behavior of different Mn
corrole complexes in sulfide oxidation using iodobenzene
diacetate.27 Taking advantage of the mild power of the oxidant,
which reduces the problem of the corrole degradation, the
authors tested different corrole complexes, bearing substituents
with differing electronic characters on the peripheral benzene
rings, to have different electron densities on the resulting Mn
complexes. Both CorrMnIII(OEt)2 and CorrMnIVCl catalysts were
tested, having the coordinated Mn in two different formal
oxidation states.
The oxidation of sulfides mainly afforded the corresponding
sulfoxides with traces of the corresponding sulfone. The
CorrMnIVCl species were more active than the corresponding
MnIII complexes and among them, the corroles with electron-
donating substituents were more efficient than the corroles
bearing electron-deficient phenyl substituents. This latter
feature can be attributed to the different oxidation potentials
of the complexes, which favor the more electron-rich species
that are more likely to be oxidized to the active form.
The greater efficiency of the CorrMnIVCl can be attributed to
a different reaction pathway with respect to the corresponding
MnIII complex, as evidenced by spectroscopic and competition
studies. In the case of the CorrMnIII complex, the oxidation
leads to the formation of the corresponding CorrMnVQO as the
active oxidant, while the formation of a more powerful oxidant,
the MnVIQO derivative, is hypothesized for CorrMnIV.
The effect of the 10-phenyl ring substituents on the oxygen
atom transfer (OAT) to thioanisole from CorrMnVQO has been
recently reported.28 In this case, both electronic and steric
effects were taken into account with the observation that
electron-withdrawing substituents accelerated the OAT process
to sulfides.
The influence of appended nitrogen ligands at the 10-phenyl
groups on the OAT process from CorrMnVQO was also investi-
gated by studying the epoxidation of alkenes.29 The rate of OAT
was significantly increased by the presence of nitrogen ligands,
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with this effect following the strength of the Mn binding. The
result can be reasonably attributed to the elongation of the
MnQO bond by the trans coordination of the N-ligand, which
destabilizes the CorrMnVQO species, enhancing the rate of the
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higher activity, but lower carbonate linkage content. Increasing
the CO2 pressure did not result in its greater inclusion in the
polymeric chain.
The Mn corroles were also tested for the polymerization

OAT process. The intramolecular binding is more effective than of epoxides and copolymerization of epoxides with cyclic
the presence of the same ligand in solution because it reduces anhydrides, showing that they are versatile catalysts for the
the competitive oxidation of the ligand. preparation of a wide range of polymeric materials.
Waser, Schöfberger, and coworkers further explored the CO2
2.2 CO2 functionalization reaction of epoxides in mild conditions, testing the catalytic
properties of different metal complexes of TPFCorr.33 Mn, FeCl,
The copolymerization of CO2 with epoxides is one of the promising
Co(PPh3), Cu, Sb(py), and Bi were the complexes tested in the
processes that use this gas as a source of materials.30 Iron corrole
reaction of CO2 with styrene oxide as the model substrate. The
derivatives were the first to be tested as catalysts for the prepara-
co-catalyst used in this case was tetrabutylammonium bromide
tion of polycarbonates by the copolymerization of CO2 with
as a nucleophilic halide source. The reaction was carried out at
cyclohexene oxide, propylene oxide and glycidyl phenyl ether.31
low temperature (60 1C) and atmospheric pressure of CO2, with
In this work, different iron corroles were used as catalysts (Fig. 4).
the aim to drive the reaction towards the formation of cyclic
For the reaction, the addition of bis(triphenylphosphoranyl-
carbonates instead of polymeric products, in this case being
idene)iminium as the co-catalyst was necessary. The products
complementary to the systems previously reported in the
obtained with cyclohexene oxide included several carbonate
literature. The results obtained showed the superior activity
groups, while with the other two monomers there were both
of the Mn complex as a catalyst and the tuning on the reaction
carbonate and ether linkages.
conditions allowed the almost complete conversion of the
TFPCorrFe(OEt2)2 showed the highest catalytic activity
starting styrene oxide under mild conditions and low catalyst
among the corrole complexes, while the importance of the
loadings. The scope of the TPFCorrMn-catalysed reaction was
corrole ligand was confirmed by the fact that the corresponding
also quite general, giving good results with different epoxides.
iron porphyrin complex afforded only the cyclic carbonate
DFT calculations, combined with spectroscopic evidence,
under the same conditions.
make it possible to formulate a plausible reaction mechanism,
In the case of glycidyl phenyl ether, it is important to note
as reported in Fig. 5.
that the copolymer obtained had crystalline behavior due to the
Recovering the catalyst at the end of the reaction and
presence of isotactic poly(glycidyl phenyl ether) units.
re-using the same complex with success demonstrated that
In a subsequent article, the same group studied the exploi-
the complex remains intact during the reaction and can be
tation of Mn corroles for the copolymerization of epoxides with
recycled for further reactions.
CO2, other than to test the same complexes in the homopoly-
merization of epoxides and their copolymerization with cyclic
anhydrides.32 TPFCorrMn was more active than TPFCorrMnCl,
even if lower than the corresponding iron corrole derivatives,
however, with the advantage of a higher content of the carbonate
linkages in the resulting polymer with both propylene oxide and
cyclohexene oxide. Also, in this case, the catalysed polymerization
needed the presence of the bis(triphenylphosphoranylidene)-
minium salt as co-catalyst. The role of the counterion was also
investigated, showing that chloride gave moderate catalyst activity
with higher carbonate linkage content, while acetate induced

Fig. 5 The reaction mechanism and calculated DFT structures of CorrMn.

Fig. 4 Molecular structure of CorrFe catalysts employed for CO2 Adapted with permission from ref. 33, which is an open-access article
copolymerization.31 distributed under the Creative Commons Attribution License (CC BY), Wiley.

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DFT investigations were further performed to elucidate the
different factors influencing the catalytic behavior of Al corroles
in the preparation of cyclic carbonates from the reaction of
CO2 and epoxides, comparing them with different metallo-
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porphyrins.34 The calculations showed a similar behavior of
the Al corrole to the analogous porphyrinates, while the
bis(triphenylphosphoranylidene)iminium iodide was calcu-
lated to be the best among the halogenated co-catalysts.
The reaction of CO2 with epoxidized canola oil catalysed by
TPFCorrMn has been used as the intermediate step for the non-
isocyanate pathway for the preparation of polyurethane.35 Poly-
urethane is obtained after the formation of the cyclic carbonate
groups in the oil by the reaction of these groups with diamines.
The exploitation of TPFCorrMn allowed the fixation of CO2
1
under mild conditions, reducing the reaction times to of the
4 License, 2019 Springer Nature.
time needed by other catalysts reported in the literature.
More recently, two articles reported the exploitation of
corrole complexes for the electrocatalytic reduction of
CO2.36,37 In the first article,36 a PEG-functionalized Co(PPh3)
corrole was used to functionalize a carbon paper electrode for
the electroreduction of CO2 to mainly ethanol in slightly acidic
water solution (pH = 6). The corrole was obtained by the reaction
of TPFCorrH3 with thiol-substituted PEG(7)–OMe groups; the
nucleophilic substitution at the para positions of the peripheral
phenyl groups afforded the corrole reported in Fig. 6.
The peripheral substitution was employed to obtain a good
dispersion of the corrole on the electrode surface. The
reduction of the complex led to the formation of a (CorrCoI)2
species; the complex was deposited on a carbon paper electrode
and it was able to catalyze the CO2 reduction to methanol and
ethanol in aqueous solution at pH = 6 (0.1 M phosphate buffer).
The catalyst was stable under the reaction conditions and the
faradaic efficiency was stable at around 48% over the reduction
process. The reaction carried out in D2O/H2O mixture indicated
that the source of the protons is the solvent, as supported by the
presence of deuterated species among the reaction products,
evidenced by GC/MS. EPR measurements indicated the presence
of a CoIII–CO2 species, supporting the reduction of CO2 to
CO2 by the (CorrCoI)2 complex. The pathways reported in
Fig. 7 illustrate the formation of the different reaction products.
Fig. 6 Molecular structure of a PEG-ylated corrole exploited for the
electrocatalytic reduction of CO2.36
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Fig. 7 Catalytic cycle for the electrocatalytic reduction of CO2 by CorrCo.
Reproduced with permission from ref. 36, which is an open-access article
distributed under the Creative Commons Attribution 4.0 International
In the second article, the Mn complex of the same corrole
was exploited to catalyze the CO2 reduction to acetic acid.37
Different from Co complexes, Mn(III) corroles have no axial
ligands and, as a consequence, the axial positions are free to
coordinate with nucleophile species for CO2 reduction. The same
conditions of the Co complex were exploited to study the catalytic
behavior of the Mn corrole. The electrochemical reduction of the
MnIIIcorrole was first metal-centered (MnIII/MnII), while the
second was ligand-centered to give a MnIIcorrole anion radical.
The second reduction wave increases under a CO2 atmosphere
and the same behavior was observed when the Mn corrole was
deposited onto the carbon paper electrode. The analysis of the
products obtained showed the presence of methanol and acetate
in solution, with H2 and CO as the gas species. Acetate was the
main product when the electrolysis was carried out at 1.25 V (vs.
Ag/AgCl), with a FE of 63%. Also, in this case, the reaction carried
out in the D2O/H2O mixture indicated the solvent as the proton
source, while the reaction in the presence of 13CO2 indicated
carbon dioxide as the carbon source for the formation of acetate.
UV-vis characterization of the species formed during the reaction
in CAN solutions suggested the formation of the [MnII(OH)2] as
the active reducing species.
Corrole derivatives have demonstrated peculiar catalytic
activity in the conversion of CO2, which is nowadays a funda-
mental need; the ability of corroles to stabilize the formally
high oxidation states of coordinated metals and to also undergo
reduction to form highly reactive complexes with metal in low
oxidation states is the key feature that justifies the superior
characteristics of corrole derivatives.
The demonstrated ability of corrole to catalyze the CO2
reduction to precious chemical products can represent a pro-
mising pathway to face this environmental concern.
2.3 Oxygen reduction reaction (ORR)
The electrocatalytic reduction of molecular oxygen to water is
one of the most important steps in the energy conversion
processes operated by devices such as fuel cells. The four-
electron redox process should be catalysed due to the slow
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kinetics and to avoid the competing production of hydrogen

peroxide; although the catalyst of choice is platinum, the high
cost of this noble metal hampers its large-scale application and for
this reason, the search for cheap and efficient catalysts is currently
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a hot research topic. Molecular catalysts can represent a promising

solution and metal complexes of corroles have been reported as
the most efficient among them. The previous works on corrole
ORR applications have been reviewed by Gross and Mahammed38
and here, we report the studies performed in the last five years.
One of the major problems to be solved for the application
of corrole complexes is to avoid the production of hydrogen
peroxide, formed as an intermediate by two-electron reduction,
and to drive the reaction towards the formation of water by a
four-electron process. Looking at the biological systems, the
first approach was to use binuclear complexes, such as co-facial
porphyrin–corrole dyads, where the proximity of two metal Fig. 9 Electropolymerization of T(4-NH2P)CorrCo(PPh3). Reproduced
centers allows the synergic 4e-reduction of the molecular from ref. 42, with permission from American Chemical Society, Copyright
oxygen.39 While the synthetic access to these dyads prevents 2018.
their wide applications, the preparation of systems where the
corrole sub-units are held close together, with the aim to induce
voltammetry (CV), obtaining conductive films on ITO-coated
the synergic reduction of O2, has been a promising approach.
electrodes (Fig. 9), chosen to obtain insights into the structure
From this point of view, the electropolymerization of tri-
of the film obtained.42
arylcorroles bearing electroactive substituents in the peripheral
The formation of the film was attributed to the formation of
positions has been proposed as a practical approach for the
pyrazine bridging units, according to the mechanism reported
preparation of efficient catalysts.
in Fig. 10, on the basis of the spectroscopic insights.
Friedman et al. reported the electropolymerization of
For the ORR process, the electropolymerization was carried
T(4-NH2P)CorrCo(PPh3); Co and Fe have been reported as the
out on a glassy carbon (GC) electrode and then on a high-
most efficient first-row transition metals for the target reaction
surface-area carbon electrode, the black pearls 2000 (BP2000).
by both theoretical calculations40 and experimental comparison
The ORR was carried out in both acidic (0.5 M H2SO4) and basic
of the performances of first-row transition metal complexes of a
(0.1 M KOH) solutions, comparing the performances of both
b-bromo-substituted corrole as electrocatalysts for the ORR in
the monomer and the electropolymerized film. The latter
alkaline solutions (Fig. 8).41
showed better catalytic activity, with an increase in the perfor-
In this study, the corrole complexes were adsorbed on
mance in basic solutions and BP-2000 electrode, where the
BP2000 electrodes. This carbon surface demonstrated a certain
process was almost completely a 4-e reduction, in particular, a
ORR catalytic activity in alkaline solutions, attributed to the
2 + 2-e process, confirming that the proximity of the macro-
quinone groups present on the BP2000 surface; Mn and Ni
cycles in the polymeric chain allowed a stepwise reduction of O2,
derivatives did not show catalytic activity for the ORR process,
as evidenced by an additional wave in the CV, typical of
while Cu corrole contributed to the catalytic process by driving
hydrogen peroxide reduction.
the reaction toward a 2 + 2e process. Co and Fe corrole
Following the same approach, a different monomer has been
complexes were the most active, able to catalyze the 4-e
more recently tested for the preparation of electropolymerized
reduction of O2 with performances comparable with those of Pt
nanoparticles.
Supported by these results, Friedman et al. carried out the
electropolymerization of T(4-NH2P)CorrCo(PPh3) by cyclic

Fig. 10 Mechanism of the formation of pyrazine bridging units. Repro-

Fig. 8 Molecular structure of corrole complexes exploited as electroca- duced from ref. 42, with permission from American Chemical Society,
talysts for the ORR in alkaline solutions.41 Copyright 2018.

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film, the 5,15-D(4-NH2Ph)10-FPCorrCo(PPh3), where in the
10 meso-position, the 4-aminophenyl group is substituted by a
pentafluorophenyl substituent.43 The introduction of the penta-
fluorophenyl group is justified by its possibility to be modified
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by the introduction of different substituents with the conse-
quent possibility of modifying both the steric and electronic
character of the polymeric chain formed by electropolymeriza-
tion of the 5,15-substituents. The electropolymerization was
performed on a GC electrode, under conditions similar to
those of the analogous T(4-NH2P)CorrCo(PPh3); although, with
only two electroactive substituents, the characterization of the
electropolymerized film showed characteristics similar to those
of T(4-NH2P)CorrCo(PPh3) in terms of both spectroscopic and
morphology features. Also, in this case, the activity of the
electropolymerized films in the ORR process was compared
with that of the deposited monomer, always showing a superior
activity. At low polymer loadings on the electrode, the electro-
chemical behavior was that of a 2-e process, while at higher
loadings the number of electrons involved increased to a
3.4 value, indicating the prevalence of the 4-e reduction. This
result confirms that the proximity of the macrocycles is impor-
tant to have a 2 + 2 e reduction process.
The influence of the peripheral substituents on the catalytic
behavior of Co corrole complexes has also been studied in
detail. b-halogenation is one of the most exploited functiona-
lizations for modifying the electronic properties of porphyri-
noids and it has been used to make more robust triarylcorroles
as oxidation catalysts. The influence of the b-halogenation of
Co corroles on their ORR catalytic activity has been studied by
depositing the complexes reported in Fig. 11 on GC and BP2000
electrodes.44
On the GC electrode, the catalytic activity of the complexes
showed the following order, both in acidic and alkaline solutions:
Co–Br8 4 Co–Cl8 B Co–H8 4 Co–F8. This result has been
rationalized in terms of combination among the contrasting
inductive electron-withdrawing and mesomeric electron-
releasing properties of the halogens. However, on a BP2000
coated electrode, where corrole complexes always show better
performances, the best results have been obtained with the
TPFCorrCo lacking b-substituents, where the reaction was mostly
involving 4-e (3.6), indicating that the peripheral substitution is
not beneficial for the catalytic activity of Co corrole.
In a further attempt to define the different parameters
involved in the corrole ORR catalysis, the influence of proton
Fig. 11 Molecular structure of b-halogenated Co corroles employed as
ORR catalysts.44
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Fig. 12 Molecular structures of Co corroles exploited as ORR catalysts.45–47
donor groups on the 10-phenyl group of the corrole Co complex
(Fig. 12a and b) has been studied.45
The rationale of the substitution was to investigate the
possible interaction of the carboxylic group with the Co ion
in the O2 coordination, driving the ORR to the desired 4-e
pathway. Also, in this case, the experiments were carried out in
alkaline and in acidic solutions, using GC and BP2000 electro-
des. In alkaline solution (0.1 M KOH) and with a GC electrode
the Co corroles catalyze the ORR via the 2-electron pathway,
with the ortho isomer showing the lowest overpotential for the
reaction.
Since BP2000 has always induced an increase in the catalytic
performances of corrole complexes, the same experiments were
repeated on these electrode surfaces. This improvement was
effectively observed, with leveling the differences of the potentials
for all the complexes but the para-isomer showed an ORR closer
to the desired 4-e mechanism (3.1). DFT calculations were
performed to elucidate the results obtained in terms of the
solvation of the Co corroles onto the BP2000 surface, which
differently stabilized the intermediate products of the O2
reduction, favoring the para complex in performing the 4-e
mechanism for the ORR process. In acidic solution, the solvation
term is less effective because of the neutral nature of the
intermediate and the favored 2-e mechanism is operative.
To investigate the mechanism of the influence of the carbon
support on the catalytic activity of the metallocorroles for the ORR,
different carbon surfaces were functionalized with Br8TPFCorrFe
and compared with BP2000, which always shows the best catalytic
behavior when functionalized with corroles for the electrocatalytic
ORR.48 The influence of the carbon surfaces on the catalytic
activity of the deposited corrole complex could be related to a
different loading of the complex, or the interactions between the
complex and surface, or, finally, to the corrole aggregation,
depending on the porosity of the surface. Spectroscopic and
microscopic investigation indicated that the porosity of the carbon
support plays a fundamental role: BP2000 has the highest amount
of 20–25 nm pore sizes, which are the right dimensions to
accommodate corrole complexes in close proximity, helping their
interactions that are critical for optimizing the ORR process.
This result evidenced the importance of the corrole dimen-
sions on the ORR catalytic activity and led the researchers to
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look to novel corrole-bearing substituents that can influence

both the electronic and size-related properties of catalysts. In
particular, the –CF3 group as the meso-substituent attracted
some attention because it is a small and strong electron-
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withdrawing substituent, two features that are particularly

promising for the target application.
For this reason, the ORR catalytic behavior of TFMCorrCo
(Fig. 12c and d) deposited on BP2000 electrode was compared Fig. 13 Molecular structure of the 10-pyrenyl-substituted Co corrole
with that of TPFCorrCo in both alkaline and acidic solutions.47 employed as the ORR catalyst.49
As previously observed, the catalytic activity, for both com-
plexes, was higher in alkaline solution, and the TFMCorrCo
showed a lower overpotential than TPFCorrCo. This feature is advantage of the strong p–p interactions is related to a faster
particularly interesting because for other species, the deposition electron transfer from the electrode to the complex, also
onto BP2000 induced a levelling of the potential values, removing improving the 4-e reduction selectivity of the O2 reduction.
the differences observed in solution.35 XPS characterization indi- Another possibility explored by the same group was to graft
cated the strong interactions of TFMCorrCo with the carbon the corrole onto the surface of CNTs by a selected functional
surface, probably through the quinone-like groups present in group. The chosen solution was to take advantage of the click
the BP2000 surface. For both complexes, the ORR mechanism chemistry route by reacting the azide-substituted 10-az-
was through a 2 + 2 e pathway. DFPCorrCo with an alkyne functionalized CNT (Fig. 14).50
To further detail the different parameters that govern the Grafting the corrole onto the CNT surface influenced the
ORR process, the influences of pH and peripheral substituents rate of the electronic communication between the macrocycle
were studied via the comparison of the catalytic behavior of and the electrode through the CNT, favoring the 4e pathway
three Co corrole complexes (Fig. 12a–c),46 with the support of for the ORR mechanism.
DFT calculations.
The study demonstrated that there is a change in the ORR
mechanism depending on the solution pH, and the variation
depends on the pKa of both the inner core N atoms and
carboxylate group, moving from a proton-controlled mechanism
at low pH to an electron-transfer-controlled mechanism at higher
pH. As a consequence, the overpotential, the stability, and the
operating mechanism of the catalyst depend on a complex
balancing of the electronic characteristics of the peripheral
substituents because high electron-withdrawing characteristics
favor the 2 + 2 or 4 e mechanism, while lower overpotential and
durability are obtained by weakening these properties.
An interesting approach for the development of efficient
ORR electrocatalysts has been the integration of corrole com-
plexes with carbon nanostructures, such as carbon nanotubes
(CNT). A route for the preparation of these hybrid catalysts is to
take advantage of p–p interactions between corroles and CNT.
For this reason, Cao and coworkers synthesized the 10-pyrene-
substituted corrole complex 10-pyrDFPCorrCo (Fig. 13) and
deposited it onto multiwalled CNTs; the performances of the
system for both the ORR and oxygen evolution were evaluated
in acidic solution (0.5 M H2SO4) and compared with those of
the unsubstituted TPFCorrCo.49
The hybrid CNT/10-pyDFPCorrCo material was deposited
onto a GC electrode and it showed significant catalytic activity
for the reduction of molecular oxygen, with a larger overvoltage
than the unsubstituted TPFCorrCo tested under the same
conditions and with a catalytic activity better than that of Pt
on carbon materials. The pyrene moiety enabled strong p–p
interactions of the complex with MWCNT, increasing the
catalytic activity and also the composite material stability. 10-
pyDFPCorrCo was not dissolved by extraction with CH2Cl2,
different from the unsubstituted corrole complex. A further Fig. 14 Structure of the corrole grafted onto CNT by click-chemistry.50

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The characterization of the grafted hybrid material, com-
pared with those obtained by non-covalent deposition of 10-
pyrDFPCorrCo and TPFCorrCo, demonstrated the reduced
loading of CorrCo for the grafted material, but rotating ring-
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disk electrode measurements showed that the number of
electrons involved in the reaction was close to 4 (3.73), slightly
higher than that of non-covalent hybrid materials. Both results
indicated the plausible ORR pathway; it is known that mono-
meric corroles catalysed the 2e reduction of O2, with the 4e
reaction thanks to the aggregation of macrocycles in the solid-
state, which allows the formation of dimeric species required
for water formation. In the case of the grafted CorrCo-CNT, the
formation of these dimeric species is not possible, and the 4e
ORR can be reasonably explained with the rapid electron
transfer rate between the corrole and the electrode. A further
advantage of the grafted system was related to the stability
because the corrole cannot be washed away by organic solvents,
as occurs for non-covalent functionalized electrodes.
The same approach was exploited for the direct functiona-
lization of Fe3O4 electrodes, following the pathway reported in
Fig. 15.51
The functionalized electrode was tested for the ORR and
Oxygen Evolution Reaction (OER) at neutral pH for their
application in Zn–air batteries. SEM and XRD characterization
confirmed the grafting of the corrole onto the villi-like electrode
surface. Electrocatalytic ORR was performed in 0.1 M phosphate
buffer at pH = 7.0. The functionalized electrode showed an
almost 4e ORR (3.97 registered e), outperforming both the
bare electrode and the electrode with the corrole simply drop
coated. The electrode was stable for 1000 CV cycles, while the
efficiency of a commercial Pt/C electrode significantly decreased
under the same conditions. These results allowed the testing of
the electrode in a Zn–air battery operating in neutral electrolyte,
showing high performance and durability, also being the first of
this kind of batteries.
A further detail that was investigated to shed light on the
ORR mechanism is related to the influence of the Co corrole
axial ligands.52 In this case, the ORR electrocatalytic
Fig. 15 Functionalization steps of Fe3O4 electrodes. Reproduced from
ref. 51, with permission from Wiley, Copyright 2019.
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performances of PPh3 and bis-py complexes of Co corrole
grafted or TPFCorrCo physically adsorbed on CNT were com-
pared in 0.1 M KOH alkaline solution (Fig. 16).
The results obtained confirmed the superior performances
of the grafted complexes and, among them, the best results
were obtained with the PPh3 complex, which presented the
lowest overpotential, with a significant difference from that of
the bis-py complex. This result is in agreement with the
importance of the electron donor ligand characteristic in the
increase in O2 binding and consequently, the electron transfer
for the ORR. On the other hand, the less efficient electrocata-
lytic activities of the dispersed TPFCorrCo derivatives were
comparable, with no significant variation among PPh3 or py
complexes. Both results can be related to the efficiency of the
electron transfer process between corrole and the electrode
surface: in the case of grafted corroles, the communication
between the corrole and the electrode is good and the influence
of ligands is important for the ORR efficiency, while for
adsorbed corroles, the less effective electron transfer becomes
the limiting factor, minimizing the influence of the axial ligand.
For bioelectrochemical devices, such as microbial fuel cells,
it is important to develop efficient ORR electrocatalysts working
in neutral solutions. For this reason, TPCorrFe and TPCorrCo
have been studied in neutral pH water solution, supported on
two different nitrogen-functionalized carbon supports, multi-
walled CNT(N) and black pearls (BP-N).53 TPCorrFeCl demon-
strated the best efficiency and, among the Co derivatives, the
bis-py complex was superior to the PPh3 counterpart. This latter
result was attributed to the lability of py ligands, which were
easily removed upon the interaction of TPCorrCo with the
nitrogen units of the carbon supports, leaving the complex
ready for O2 binding, with the same process being more
difficult for the analogous PPh3 complex. This hypothesis is
also supported by the superior characteristics of BP-N to
CNT(N) because of the higher content of pyridinic nitrogens
on the BP-N surface, which makes the coordination of the
corrole complex easier.
The best efficiency of the TPCorrFeCl can be related to the
aggregation that the catalyst undergoes on the carbon support,
as evidenced by UV-vis spectra, which is not present in the Co
derivative. This aggregation can also explicate the efficiency in
driving the ORR to the 4e mechanism.
The influence of the ligand structure on the ORR electro-
catalytic activity of iron complexes has been recently reported,54
where the performances of different iron complexes (Fig. 17)
have been compared and the results obtained have been
rationalized by using both spectroscopic techniques and DFT
calculations. For the majority of these complexes, including
corrole, the ORR followed a 4e mechanism, while the electro-
catalytic activity followed the sequence FeTAA 4 FePc 4 FeTPP
4 FeCorrole 4 FeTim 4 FeSalen. The high oxidation state and
increased spin density on the coordinated iron, as determined
by XANES and Mössbauer spectroscopy, were indicated as the
factors influencing the ability to catalyze the O–O bond and
consequently the ORR electrocatalytic activity, which was sup-
ported by DFT calculations.
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Fig. 16 Molecular structures and deposition techniques for the grafting and dispersion of Co corroles on CNT.52
The catalytic activity of TPFCorrCo(py)2 for the 2e/2H+
reduction of molecular oxygen to hydrogen peroxide by ferro-
cene or 9,10-dihydro-10-methylacridine was demonstrated.55
While the interest in the ORR has been devoted to improving
the 4 e pathway, it should also be noted that the production of
hydrogen peroxide is of interest for different applications.
The spectroscopic analysis of the reaction allowed the
determination of the mechanism of the catalytic cycle. The
HClO4 leads to the removal of the py axial ligands with
the formation of the tetra-coordinated TPFCorrCo, which, in
acidic conditions, is oxidized to the corresponding p–cation
radical complex, with the formation of O2H. In the case of
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ferrocene, this proton-coupled electron transfer was the rate-
determining step of the reaction. The mechanism of the
catalytic cycle is reported in Fig. 18.
When ferrocene was replaced with acridine, a 2e reductant,
the rate-determining step became the electron transfer to the
reductant. The titanyl complex of TPPH2 was used to detect the
H2O2 formation, showing an almost 100% efficiency.
2.4 Water oxidation
Water oxidation is an important process for energy conversion,
admirably performed in Nature by Photosystem II. In this
process, the oxygen evolution reaction (OER) is the kinetically
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Fig. 19 Axial Ligands of TPFCorrCo employed to study their influence on

the OER catalytic activity.56

TPFCorrCo undergoes two oxidation waves; the first one is

mostly ligand centered, as evidenced by spectroscopic charac-
terization, with UV-vis showing a significant decrease in the
Soret and Q bands, and EPR showing a signal of an organic
radical. These features indicated the formation of a Co(III)
corrole p–cation radical species. The second wave is responsible
for the water oxidation, and it showed a strong dependence on
the donor characteristics of the axial ligand. Electron donor
ligands make the catalytic activity of TPFCorrCo more efficient,
with lower overpotentials and higher catalytic current. The
proposed catalytic cycle is reported in Fig. 20.
The trans ligand is proposed to weaken the CoQO bond,
favoring the subsequent attack of the water molecule.
Gross and coworkers studied in detail the mechanism of
Fig. 17 Molecular structures of iron complexes tested as ORR the OER, investigating the nature of the intermediates, using
electrocatalysts.54
TPFCorrCo as the catalyst.57 The comparison of the CVs of
TPFCorrCo and the analogous TPFCorrAl provided information
on the oxidation products. For TPFCorrCo, the oxidation can be
both ligand- or metal-centered, in the case of the Al counterpart,
only ligand-based processes are possible. The spectroelectro-
chemical analysis allowed the confirmation that while the first
oxidation is ligand centered, the second wave also involves the
metal by electron transfer from the coordinated cobalt to the
doubly oxidized corrole. To investigate the pH effect on the OER,
TBAOH was added to the TPFCorrCo solution; the effect obtained
was an increase in the catalytic activity, with the emergence of a
second oxidation wave in the CV spectrum (Fig. 21).
This result suggested the presence of a second water oxidiz-
ing species in basic conditions. The hypothesis is the binding

Fig. 18 The catalytic cycle for the ORR catalysed by TPFCorrCo.55

slow process that limits the efficiency of water splitting and,

considering that this reaction is the reverse of the ORR, metal
complexes of corrole have also been studied to catalyze this
process, in some cases for both ORR and OER.
For this reason, Cobalt corrole complexes have been inten-
sively studied, with TPFCorrCo as the prototypical example.56
Also in this case the effect of the trans ligand on the efficiency of
the OER has been investigated.56 The substituted pyridines and
the other donor compounds reported in Fig. 19 were tested as
axial ligands of TPFCorrCo. Fig. 20 The catalytic cycle for the ORR catalysed by TPFCorrCo.56

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Fig. 21 CV spectra in water/acetonitrile solution with (continuous line)
and without (dotted line) TPFCorrCo in different amounts of TBAOH.
Reproduced from ref. 57, with permission from the American Chemical
Society, Copyright 2018.
of hydroxide as a ligand and to obtain more insight into this
hypothesis, TBAOH was replaced with TBAF. Also, in this case,
two oxidation waves were observed, requiring a smaller amount
of TBAF, indicating that the coordination of F to the Co center
in this case also led to the formation of the additional oxidizing
species. EPR characterization showed, however, that in the case of
hydroxide addition a cobalt superoxide complex (TPFCorrCoO2)
was formed, by a first reduction of the Co center operated by OH,
then the formed Co(II) binds molecular oxygen to form the super-
oxide species.
The influence of peripheral substituents on the efficiency of
the OER has also been investigated. Substituents bearing
pendant phosphonic groups were introduced at the 10-
position of a 5,15-bis(pentafluorophenyl)corrole (Fig. 22).58
The electrocatalytic OERs were performed by the deposition
of the complexes onto FTO electrodes and the reaction was
carried out in phosphate buffer solutions at pH = 7. The
CH2PO(OH)2 derivative showed the best performance, with a
small overpotential value. The substituent effect is related to its
action as an intramolecular base helping the formation of the
O–O bond. The same result was obtained using GC electrodes.
The importance of the formation of corrole–CNT hybrids on
the electrode surface for the OER and Hydrogen Evolution Reaction
(HER) catalytic efficiencies was investigated in a wide pH range.59
Both covalent grafting (Fig. 23) and simple dispersion (Fig. 24)
were exploited with the Co corroles reported in the figures.
Fig. 22 Molecular structures of functionalized Co corroles exploited as
OER catalysts.58
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The CV characteristics of the three Co corrole complexes
were similar in acetonitrile solution. The hybrid corrole–CNT
materials, obtained by covalent attack for azidocorrole and
supramolecular interaction for pyrene and unsubstituted cor-
role, were deposited on GC electrodes and their efficiencies for
both the OER and HER in acidic (0.5 M H2SO4) and basic (1 M
KOH) solutions were investigated. In both cases, the shortest
grafted corrole gave the best results, followed by similar pyrene
and long grafted corroles and with TPFCorrCo being the less
efficient. Also, in this case, the result obtained can be attributed
to the best electronic communication between the hybrid
material and the electrode, as in the case of the ORR. It is,
however, worth noting that the catalytic system was efficient for
both the HER and OER in a wide pH range, being the first to
perform in this way.
Another feature investigated for developing optimized
catalysts for the OER is the influence of the electronic character
of the meso aryl substituents. While TPFCorrCo has been the
reference complex for these studies, it is known that electron-
donating substituents will favor the OER. For this reason, two
4-amino phenyl groups have been introduced at the 5,15-
positions of the corrole ring to obtain the DAFPCorrCo(py)2.60
The CV of the complex in acetonitrile showed two oxidation
and two reduction peaks. The electrocatalytic behavior of
DAFPCorrCo(py)2 was demonstrated in acetonitrile in the
presence of water and TFA. While the first oxidation and
reduction peaks were not affected by the presence of water
and TFA, the second oxidation peak registered the OER and the
second reduction peak, the HER. The performances for these
reactions were then studied in heterogeneous conditions, by
depositing DAFPCorrCo(py)2 onto the surface of a GC electrode;
the experiments were carried out in acidic (0.5 M H2SO4) and
basic (KOH 1 M) solutions. Also, in this case, it was possible to
observe the catalytic activity of the complex for both the OER
and HER, with low overpotentials for both of them.
The OER catalytic activities of the 5,15-dpM-10oMCorrCo(py)2
and 5,15-DN-10oMCorrCo(py)2 (Fig. 25) were also investigated to
explore the influence of the meso aryl substituents.61
The presence of meso aryl groups with fewer electron-
withdrawing characteristics than the usual pentafluorophenyl
substituents led to the observation of a third oxidation wave in
the CV carried out in acetonitrile. The electrocatalytic activity of
the complexes was studied in acetonitrile in the presence of
water in homogeneous conditions and the OER was detected
for the third oxidation wave. The O2 evolution for the process
was confirmed by GC and with Clark electrode measurements
in heterogeneous conditions, depositing the complexes onto
FTO electrodes. The turnover frequency (TOF) measured was
higher than that of those measured with TPFCorrCo or
DAFPCorrCo(py)2. The potentials necessary for the OER, in this
case, were higher than those in literature but it should be noted
that in this case the third oxidation wave was exploited, while
for TPFCorrCo or DAFPCorrCo(py)2, the OER was observed for
the second oxidation wave. However, the impact of this
potential limitation can be lowered by the observation that
the potential of this process is strongly influenced by the nature
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Fig. 23 Preparation pathways for the covalent grafting of Co corroles onto CNTs.59
of the axial ligand and a significant shift at a lower potential for
the third oxidation wave was observed by increasing the water
concentration, indicating the substitution of py with H2O as the
CorrCo axial ligand. These results indicate a potential route for
the optimization of the catalyst efficiency, by tuning the elec-
tronic characteristics of the corrole peripheral positions.
The selectivity of the OER towards the production of H2O2 has
also been recently investigated.62 Although the water oxidation to
O2 is thermodynamically favored, the formation of H2O2 has also
been reported and its production can also be of practical interest.
As such, the octabromo-substituted 5,15-dpM-10oMCorrCo(py)2
and 5,15-DN-10oMCorrCo(py)2 were studied.
The electrochemical behavior of this complex in acetonitrile
was different depending on whether the conditions were
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homogeneous or heterogeneous. In homogeneous conditions,
two oxidation waves were observed for Br8TPFCorrCo (Fig. 26)
and the addition of an aqueous base led to the current increase
for the second oxidation wave, indicating the presence of a
catalytic process. In these conditions, the evolution of O2 with
an 18% faradaic yield was observed, while 70% of H2O2 was
detected in solution, indicating that the production of hydro-
gen peroxide is favored in homogeneous conditions.
On the other hand, Br8TPFCorrCo was deposited onto an
edge-plane graphite (EPG) electrode and in this case, the water
oxidation exclusively produced molecular oxygen without
evidence of H2O2. Spectroelectrochemical and EPR characteriza-
tions gave some insight into the reason for this different
behavior. The oxidation of Co corrole in both cases affords the
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[Cor +–CoIII–O ] intermediate. This species undergoes the

nucleophilic attack by the hydroxide ion to give [Cor +–CoIII–
OOH]. In homogeneous conditions this intermediate is hydro-
lyzed by water, giving H2O2 and [Cor +–CoIII–OH], before being
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oxidized and affording O2. In heterogeneous conditions, the

electron transfer is faster and for this reason, the formation of
[Cor +–CoIII–OO ] is prompt, leading to the O2 evolution.
While cobalt corrole complexes have been intensively stu-
died as catalysts for the OER, only a few reports have been
published on different metal complexes. The Mn complex of a
water-soluble derivative of TPFCorrH3 (Fig. 27) was deposited
onto the edge-plane pyrolytic graphite electrode and O2 evolu-
tion was observed by increasing the pH of the buffer solution.63
This complex was also able to reduce the O2 produced
during the reverse scan, demonstrating a bifunctional charac-
ter. The complex was stable under the reaction conditions and
the good faradaic efficiency of the related OER makes it a
promising catalyst for water oxidation.
More recently, iron corroles have been tested as water
oxidation electrocatalysts.64 For this purpose CorrFeCl derivatives,
bearing different meso aryl substituents, have been studied,
together with the corresponding m-oxo dimers and the TPFCorr
b–b0 linked dimer (Fig. 28). Their performances were then com-
pared with those of the corresponding Co(py)2 complexes.
For all the species, the CV characterization showed that the
Fig. 24 Dispersion of Co corroles onto CNTs.59
electronic character of the meso aryl substituents influenced the
potential waves, with TPCorr derivatives being more likely to be
oxidized and more difficult to be reduced. The m-oxo dimers
showed a marked difference in the potential waves, undergoing
shifts to lower values, while the b–b 0 dimers showed no
significant variations with respect to the corresponding mono-
mers, indicating the absence of electronic interactions between
the two subunits.
The OER was observed for iron complexes at potentials
higher than 1 V, with the lowest value necessary for TPCorr-
FeCl. However, the best catalytic efficiency was obtained with
the fluoro-substituted corroles. For Co derivatives, the same
trend was observed and TPCorrCo was not able to catalyze the
OER. For the dimers, while the m-oxo derivatives of Fe were
shown to be less useful for the OER, the linear dimers demon-
strated promising performances, with the dimer being superior
to the corresponding monomer for the Co derivatives.
Fig. 25 Molecular structures of Co corrole complexes exploited as OER When the complexes were deposited on the surface of
catalysts.61 Nafion-coated FTO electrodes, the evolution of O2 was clearly
visible upon the application of positive potentials to the water

Fig. 26 The molecular structure of Br8TPFCorrCo employed as an OER Fig. 27 The molecular structure of the water-soluble Mn corrole studied
catalyst.62 as a catalyst for the OER.63

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Fig. 28 Molecular structures of Co and Fe corroles tested as water

oxidation electrocatalysts.64

buffer solutions. TPFCorrFeCl showed a catalytic efficiency

similar to that of the corresponding Co(py)2 complex, while in
this case, the linear dimeric species showed lower efficiencies.
The results obtained demonstrated that iron corroles can have Fig. 29 Molecular structures and CV spectra of metal corrole complexes.
Adapted from ref. 65, with permission from the Royal Society of Chemistry,
promising roles as electrocatalysts for the OER.
Copyright 2020.
Recently, Co, Mn, and Cu complexes of TFPCorrH3 and
T(2,6-F2)PCorrH3 were tested as redox mediators for the OER
in Li–O2 batteries.65 The role of these species is to be easily oxidized
and in this form, they should oxidize the Li2O2 formed as the ORR
product in the cell. A drawback that limits the efficiency of these
cells is the instability of the redox mediators.66 The CV of six
different corrole complexes were investigated in the diglyme
solution used in Li–O2 batteries (Fig. 29).
From the CV, it was possible to determine that Cu complexes
have the best characteristics for the target application. This
hypothesis was confirmed by the comparison of the CV char-
acteristics of the corroles together with those of some used
redox mediators. After 50 cycles T(2,6-F2)PCorrCu showed the Fig. 30 The catalytic cycle of T(2,6-F2)PCorrCu in Li–O2 batteries.
Adapted from ref. 65, with permission from the Royal Society of Chemistry,
highest stability and it was also tested in the presence of O2 in
Copyright 2020.
conditions that can induce the formation/decomposition of
Li2O2; in this case, no evidence of decomposition was observed,
as confirmed by UV-vis analysis of the complex. A cycle was
proposed for the catalytic action of T(2,6-F2)PCorrCu, as 2.5 Hydrogen evolution reaction (HER)
reported in Fig. 30. Metal complexes of corroles have also been exploited for the
To further confirm the superb performance of T(2,6-F2)PCorrCu HER, which is another important process for energy conversion
as a redox mediator, the complex was exploited in a Li–O2 cell, and is frequently coupled with the OER in the water-splitting
cycled more than 100 times, again showing stability in the process. Consequently, for this reaction, some of the complexes
operative conditions. already tested for both the ORR and OER have also been involved

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in the HER; 10-pyrDFPCorrCoPPh3 supported on graphene has

been exploited as an electrocatalyst for the HER.67 The electro-
catalytic activity of 10-pyrDFPCorrCoPPh3 was compared with
that of 10-pyrDFPCorrCo(py)2 and TPFCorrCo(py)2, with all the
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complexes loaded on graphene as the support and deposited

onto GC electrodes; the experiments were carried out in aqueous
solutions with pH ranging from acidic to basic conditions. In this
way, it was possible to compare the influence of the pyrene
substituent, the axial ligand, and the pH of the solution.
The measurements were first carried out in homogeneous
conditions in acetonitrile, using benzoic acid as the proton
source. The second reduction wave of complexes showed a
catalytic current, confirming that Co(I) is the catalytically active
species as proposed in the literature.68 Fig. 31 Molecular structures of trans-A2B Co corroles employed as HER
10-pyrDFPCorrCoPPh3 showed the highest current under catalysts.69
the same reaction conditions; the proposed importance of the
electron donor effect of the trans ligand, which facilitates the
protonation of the Co(I) species formed in the second reduction on the HER and ORR electrocatalytic activity of Co corroles were
wave, could be disputed by the loss of the axial ligand that reported (Fig. 32).70,71 In the first article,70 the Suzuki–Miyaura
Co(III) corroles undergo upon reduction.16 On the other hand, coupling reaction was carried out on corroles bearing the 4-Br
TPFCorrCo(py)2 produced a higher current than 10-pyrDFP- substituent selectively at one (10-), two (5,15-) or all the meso
CorrCo(py)2 because the electron-withdrawing character of the positions, with the aim to detail the influence of both the
10-pentafluorophenyl group leads to an easier reduction of the substituent addition and the relative position on the corrole
complex with the formation of the active catalytic intermediate. ring. The complexes were mixed with reduced graphene oxide
In heterogeneous conditions, the complexes were immobi-
lized on graphene and the hybrid materials deposited on GC
electrodes. The electrocatalytic activity was tested in aqueous
solutions having different pH values: H2SO4 0.5 M for acidic
conditions, neutral 0.1 M phosphate buffer, and 0.1 M KOH as
the basic medium. The complexes were stable in these condi-
tions and in all cases, 10-pyrDFPCorrCoPPh3 showed the best
catalytic efficiency. This demonstrated once again the influence
of the donor characteristics of PPh3 in the catalytic mechanism.
Different from homogeneous conditions, 10-pyrDFPCorrCo(py)2
showed, in this case, higher currents than TPFCorrCo(py)2,
which indicated the importance of the pyrenyl substituent in
giving strong p–p interactions between corrole and the graphene
support, so leading to a faster electron transfer between the
corrole and the GC electrode.
The influence of the meso aryl substituents on the HER
electrocatalytic efficiency of Co corrole derivatives has also been
investigated.69 Seven 5,15-bis (3-nitrophenyl)-corroles bearing differ-
ent halogen-substituted phenyl rings at the 10-position have been
prepared and tested for the HER in acidic conditions (Fig. 31).
In these conditions, the HER was observed for both the first
and the third reduction waves, centered on formal CoIII/CoII
and CoII/CoI processes, while the second reduction is in charge
of the peripheral nitro groups. The catalytic current intensity of
these processes depends on the acid concentration, with an
increase at the third reduction with an increase in the acid
concentration, and on the nature of the 10-phenyl substituent.
The electron-withdrawing character increased the catalytic
efficiency, with the 10-pentafluorophenyl corrole derivative
being the most efficient.
Following this approach, the effects of the expansion of the Fig. 32 Molecular structures of meso-expanded Co corroles exploited as
meso-aryl substituents by the Suzuki–Miyaura coupling reaction HER and ORR electrocatalysts.70

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(rGO) and then deposited onto GC electrodes. The electro-
catalytic activity was studied in a 0.5 M H2SO4 solution for
HER and 0.1 M NaOH solution for ORR. The results obtained
showed that the meso-substituent expansion is convenient for
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increasing the catalyst efficiency and that the expansion at the
10-position is the most effective. Regarding the electronic
characteristics of the substituents, in this case, the electron
withdrawing feature is the most effective for HER. The com-
plexes were also tested in the catalysis of the ORR in both acidic
and basic solutions; a positive shift of the potentials and an
increase in the electrocatalytic activity with respect to the
reference TPCorrCoPPh3 were observed.
The same approach was recently exploited in the ring
expansion at the 3-Br phenyl-substituted Co corrole complexes
(Fig. 33).71 The complexes were tested under the same condi-
tions as the corresponding para-isomers and in this case, the
effect of the aryl substituents was slightly different; also the
4-nitrophenyl was again the most efficient at promoting an
increase in the HER catalytic efficiency. The effect of the
substituent expansion was stronger in this case than previously
observed for the corresponding para-isomers.
Using similar experimental conditions, the influences of the
electronic characteristics of the meso aryl substituents were
investigated.72 In this case, the Co complex of trans-A2B cor-
roles having electron-withdrawing or electron-releasing substi-
tuents at the 10-position, together with the reference phenyl
group, were prepared and tested as electrocatalysts for both the
HER and ORR (Fig. 34). It was found for both reactions that
the best performances were obtained for the complex having
the electron-releasing group at the 10-position, opening the way
for a novel push–pull strategy for the development of superior
electrocatalysts.
The homogeneous HER was attempted using TECorrCo(py)
in acetonitrile/water (2 : 3) solution.73 The electron-withdrawing
characteristics of the meso ethoxycarbonyl groups and the
improved solubility in the water mixture were the reasons for
the corrole choice.
The CV of the complex was in agreement with other Co corrole
behaviors, with the second reduction at 1.39 V vs. Ag/AgNO3
attributed to the formal CoII/CoI process. The electrocatalytic
Fig. 33 Molecular structures of Co corroles.71
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Fig. 34 Molecular structures of 10-substituted Co corroles studied as
HER and ORR catalysts.72
activity was tested in DMF, using acetic acid as the proton
source. A catalytic current was observed at 1.39 V, confirming
that CorrCoI is the catalytic active species. The measurements
were then carried out in aqueous phosphate buffer (pH = 7),
which demonstrated that TECorrCo(py) is also catalytically
active for the HER in these conditions. The current was
dependent on the pH of the buffer and TECorrCo(py) was stable
under electrolysis and was recovered intact at the end of the
process.
The photocatalytic production of H2 was also investigated
using TECorrCo(py) as the photocatalyst in a three-component
system, which included [Ru(bpy)3]Cl2 as the photosensitizer
and ascorbic acid as the electron donor. The visible-light
irradiation of a buffer solution at pH = 4.5 demonstrated the
evolution of H2, with the amount depending on the concen-
tration of the catalytic system. The results obtained showed
moderate photocatalytic activity of TECorrCo(py).
The photocatalytic production of H2 was also investigated
using Co and Fe derivatives of the corroles reported in Fig. 35,
dispersed on MWCNTs as catalysts.74
In this work, terphenyl was exploited as a photosensitizer
and triethylamine as a sacrificial electron donor. The photo-
catalytic production of hydrogen was first carried out by dis-
solving corrole, terphenyl and triethylamine in dioxane under
UV irradiation. The H2 evolution was observed upon water
Fig. 35 Molecular structures of the A3 corroles dispersed on MWCNTs.74
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addition. The mechanism of the reaction followed different The influence of peripheral substituents on the electrocata-
steps, as described below: lytic activity of cobalt corrole has been investigated on four
hn
complexes (Fig. 36).76
TP ƒ! TP In this case, the reaction of ethanolamine with TPFCorrCo
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and 10-PhDPFCorrCo led to the substitution of the para-

TP* + Et3N - TP  + Et3N + fluorine atoms with ethanolamine groups.
The electrocatalytic activities of these complexes for the HER
[MI(Cor)]2 + Et3NH+ - H[MII(Cor)] + Et3N were first investigated in acetonitrile solution in the presence of
acetic acid as the proton source. In these conditions, the
H[MII(Cor)] + Et3NH+ - [MI(Cor)] +H2 + Et3N second reduction of the complexes became irreversible, indi-
cating that the CoI corrole species is catalytically active. The
Et3N + + Et3N - Et3NH+ + Et2NCHCH3 wave shifted positively, indicating the formation of the CoIII–H
complex. Increasing the acetic acid concentration did not
Et2NCHCH3 + [MIII(Cor)] - Et2N+ + CHCH3 + [MII(Cor)] induce a significant increase in the catalytic current but led
to the appearance of an additional catalytic wave as the result of
TP  + [MIII(Cor)] - TP + [MII(Cor)] the CoIII–H/CoII–H process and this reduced species interacted
with protons to furnish H2. A multi-way catalytic cycle was then
TP  + [MII(Cor)] - TP + [MI(Cor)]2 proposed (Fig. 37). Electrolysis at controlled potential demon-
strated that ethanolamine-substituted complexes showed the
Co corroles were more efficient for the HER than the highest TOF, probably because the ethanolamine groups can
corresponding Fe analogs and, among corroles, the TNPCorr induce a larger electron density on the corrole nucleus,
gave the best performance. In these conditions, the Co corrole
was not stable and decomposed at the end of the reaction, with
the authors proposing the hydrogenation of the macrocycle.
Although the use of TP, which has a high reduction potential,
reduced the catalytic efficiency difference of the various com-
plexes, the reaction carried out without the photosensitizer
showed that the electron withdrawing character of the peripheral
aryl groups increased the catalytic properties of the complex.
With this result, the TNPCorrCo was dispersed onto
MWCNT and the obtained hybrid photocatalyst was tested for
H2 production in the same conditions. Significantly higher
amount of H2 were obtained with the hybrid material, and it
is important to note that MWCNT did not produced H2 without
TNPCorrCo. The system was even more efficient in formate
buffer at pH = 3, due to the higher proton concentration in this
solution. The results obtained were comparable with those
obtained in literature by electrocatalysis. The observed
improvements were attributed to the electron transfer ability
of MWCNT, which accelerated the formation of the CorrCo
catalytic active species.
The photoelectrocatalysis was also attempted, by application
of a difference of potential under irradiation, obtaining an increase
of H2 production. Probably the light irradiation accelerates the
electrons flow, with also in this case a faster formation of the
reduced CorrCoI active species. The catalyst however was decom-
posed after 30 min under photoelectrocatalysis.
TNPCorrCoPPh3 has been more recently investigated for
electrocatalytic HER.75 The electrocatalytic activity was first
studied in DMF using acetic acid as a proton source and
comparing the performances with those of the unsubstituted
TPCorrCoPPh3. The nitro substituted complex showed superior
catalytic characteristics, confirming also in this case the influence
of the peripheral electron-withdrawing substituents. The complex
was also able to catalyze HER in aqueous neutral phosphate
buffer solution and it was stable under electrolysis for 3 days. Fig. 36 Molecular structures of functionalized TPFCorrCoPPh3 complexes.76

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Fig. 37 Catalytic cycle for hydrogen production by Co corroles.76

facilitating hydrogen evolution. A similar pathway was

observed using TFA as the proton source for TPFCorrCo and
10-PhDPFCorrCo but in the case of triethanolamine-substituted
corroles, the increase in the TFA concentration led to the
increase of the second reduction wave, with the direct CoIII–H
involvement for the H2 production.
The HER in aqueous medium was investigated, dissolving
the catalysts in acetonitrile/water solution (2 : 3 v/v). The com-
plexes were able to catalyze the HER in water and the hydrogen
evolution increased with lowering the pH. A complex interplay
of the steps reported in Fig. 40 contributed to the reaction.
Following the same approach, four different PPh3 Co complexes
of corroles (Fig. 38) have recently been investigated for the HER.77 Fig. 38 Molecular structures of functionalized CorrCo.77

The electrocatalytic activities of these complexes were first

tested in DMF using acids of different strengths as proton sources:
acetic acid, TFA and pTsOH. Different behaviors were observed
depending on the acid used, which indicated different pathways
for the HER mechanism. In all cases, the acid addition changed
the second reduction wave, indicating that the catalytic active
species is the CoI complex. With acetic acid, the reduced corrole
was protonated to give the CoIII–H species, with the formation
confirmed by 1H NMR spectroscopy. This species needs further
reduction to produce H2, as indicated by the presence of the
second reduction wave in the CV, with an additional process at
more negative potential; the mechanism reported in Fig. 39 has
been proposed, according to the CV evidence.
Using TFA, the second reduction wave indicated an irrever-
sible process and the variation observed on increasing the acid
concentration indicated the coexistence of the two catalytic
processes reported in Fig. 39. Furthermore, two additional Fig. 39 Multi-way catalytic cycle for the HER catalysed by CorrCo.77

waves attributable to the peripheral pyridine and amide groups

were observed for peripherally-functionalized corroles, both
groups cooperating to give the HER. With pTsOH, the behavior
was similar to that of TFA.
The electrocatalytic activities of these complexes were then
tested in an aqueous environment, represented by a 2 : 3
mixture of acetonitrile/water. While high TOFs were observed
for all the complexes, the best performance was obtained for
pAldDPFCorrCo. All the complexes were stable in the electro-
lytic conditions, being recovered intact after 6 h of electrolysis.
While Co corroles have been the complexes most intensively
studied for the HER, recently, attention has also been addressed
to copper derivatives. The first example exploited copper com-
plexes of 5,15-bis (3-nitrophenyl)corroles bearing aryl groups at
the 10-position with a different number of fluorine atoms,
similar to those studied as Co complexes (Fig. 31).78 The HER
was studied in benzonitrile, using TFA as the proton source; the
stability of copper corroles in these conditions was confirmed by

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Fig. 40 Molecular structures of 10-functionalized CorrCu.79
checking the invariance of the UV-vis spectra over 4 hours. The
addition of TFA induced a catalytic wave at a potential close to
the first reduction of the complexes, with the current increasing
with the increase in the acid concentration. The best perfor-
mances were obtained with the corrole having the pentafluor-
ophenyl substituent at the 10-position. A further study was
carried out later by the same group, investigating copper com-
plexes of trans-A2B corroles reported in Fig. 40.79
The HER was also studied in benzonitrile using TFA as the
proton source; it was observed that while the first reduction
showed a slight increase in the catalytic current, a significant
catalytic wave was observed beyond the second reduction, with
the 10-pentafluorophenyl-substituted corrole complex as the
most active catalyst.
More recently, Gross et al. reported the HER behavior of
TPFCorrCu complexes b-substituted with trifluoromethyl groups
(Fig. 41).80
The performances of these complexes as electrocatalysts for
the HER were studied in acetonitrile using TFA as the proton
source. The second reduction wave changed significantly by the
addition of TFA, while the first reduction process remained
almost unchanged. The b-trisubstituted corrole was better than
the b-four substituted, showing higher TOF and lower onset
potential. Both of them performed much better than the
unsubstituted TPFCorrCu. The complexes were stable in the
acidic conditions for 24 hours in the dark, confirming their
electrocatalytic activity for the HER in controlled potential
electrolysis experiments. Attempts to characterize the nature
of the product of the second reduction, as the (CorrCu)2, were
Fig. 41 b-CF3-functionalized CorrCu as HER catalysts.80
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Fig. 42 The proposed catalytic cycle for the HER catalysed by free-base
corroles.65
unsuccessful, not allowing the confirmation of the hypothesis
of a catalytic mechanism similar to that of Co complexes.
However, it is interesting to note that the same CV behavior
observed for Co and Cu complexes led Kadish et al. to propose
similar redox processes for these complexes, with a non-innocent
character also present for Co corrole derivatives.81 This is further
support for a similar HER catalytic mechanism for these derivatives.
Even free-base corroles have been proposed as electrocata-
lysts for the HER. It has been reported65 that the free-base
corroles were investigated as electrocatalysts for the HER.
The same electrochemical conditions for the HER were
exploited and the free-base corroles were demonstrated to
catalyze hydrogen evolution, and a complex catalytic mechanism
was proposed, according to the results obtained (Fig. 42). Two
different pathways were proposed for ethanolamine-substituted
corroles with respect to the other species and the differences were
justified by the presence or not of the protonation of corrole free-
bases in the presence of TFA.
The free-base corroles were not stable under the electrolysis
conditions and were decomposed during catalysis.
A detailed study of the electrocatalytic activity of TPFCorrH3
has been recently reported.82 The HER was studied in acetonitrile,
using p-TsOH and benzoic acid as the proton sources. Without
acid, TPFCorrH3 showed two reduction waves, corresponding to
the formation of the mono and dianion corrole. The addition of p-
TsOH induced a cathodic shift in the reduction potentials, with a
catalytic wave increasing with the increase in the acid concen-
tration at the second reduction potential. No catalytic activity was
observed when benzoic acid was added, indicating that the acid
strength is fundamental for the HER. DFT calculations, spectro-
scopic and spectroelectrochemical experiments allowed the for-
mulation of the following mechanistic pathway:
CorrH3 + HA - CorrH4+ + A
CorrH4+ + e - CorrH4
CorrH4 + e - CorrH4
CorrH4 - CorrH2 + H2
CorrH2 + HA - CorrH3 + A,
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with the process starting with the formation of the protonated

corrole, which can then be reduced, leading to H2 evolution.
First-row transition metal complexes of corrole have been
demonstrated to be the most efficient alternatives to Pt catalysts
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for these important clean energy conversion processes, i.e., the

ORR, OER, and HER. The versatility of the corroles in stabilizing
both high oxidation states and reactive low oxidation states for
coordinated metals makes them suitable for catalyzing the activa-
tion of small molecules, with Fe and Co complexes usually being
the most active. Furthermore, the possibility of tuning the proper-
ties of corrole catalysts by synthetic modifications can allow the
optimization of their characteristics, although a rational method
for comparing the different results reported in the literature
should be defined, to provide guidance in the target modifications
and to avoid the ‘‘try and see’’ approach, which will result in a
delay in the practical applications of these catalysts.

2.6 Miscellaneous reactions

Corrole complexes have also been exploited as catalysts in other
reactions. TPFCorrCo(PPh3) has been tested as a catalyst for the
hydration of terminal alkynes.83
Phenylacetylene was first used as model in this reaction
carried out in methanol/H2SO4 medium, affording acetophenone Fig. 44 The catalytic cycle of heterocycle formation catalysed by por-
phyrin Co complexes.84
as the reaction product. A complete conversion was obtained with
the catalyst in a 0.3% molar ratio but optimization of the reaction
conditions allowed 90% conversion with the TPFCorrCo(PPh3)
Three different corrole complexes were tested (Fig. 45) to
concentration reduced by one order of magnitude. The increase
demonstrate the influence of the electronic character of the
in the H2SO4 concentration did not induce the decomposition of
peripheral substituents on the catalytic activity. CV character-
the catalyst. The scope of the reaction was quite good, working
ization of the complexes allowed the choice of the right
with both alkyl and aryl terminal alkynes, although electron-
chemical reductant, able to form the first reduction species
donating substituents afforded higher yields. The scale-up of the
under the catalytic reaction conditions, which was cobaltocene
reaction to 10 g showed an appreciable 90% yield; recycling the
for TPCorrCo and Br2TPCorrCo and decamethylcobaltocene for
catalyst at the end of the reaction afforded an 87% yield,
TMesCorrCo.
indicating the stability of TPFCorrCo(PPh3) under the reaction
The catalytic activity of these corroles was tested in the
conditions.
reaction pathway previously reported; for all complexes in
One-electron reduced Co corrole anions have been exploited
toluene, the reagent was completely converted and the highest
as catalysts for the formation of heterocycles by the ring closure
yield of pyrrolidine was reached with TPCorrCo, with no linear
C–H amination reaction (Fig. 43).84
product being obtained. In the absence of both reductant and
Considering the reaction mechanism for the reaction cata-
Boc2O, the reaction did not take place, indicating that the
lysed by analogous Co-porphyrin complexes (Fig. 44), it was
presence of the reduced cobalt corrole is necessary for reaction
surmised that the use of the reduced Co–corrole, with an
success. Although the reaction was much faster than that
increased charge density of the metal center, could help the
observed with analogous porphyrins, confirming the initial
rate-determining step of the reaction, which is the N2 evolution,
hypothesis, it should be noted that 2 hours were necessary
with consequent oxidation of the Co.
for the reaction to start, which was attributed to the low
solubility of the anionic reduced corrole species in toluene.
Attempts to use more polar solvents for the reaction were
however not successful. It should be noted that the best yield
was obtained with TPCorrCo, in contrast to the expected
influence of peripheral substituents; however, both steric
effects and the different solubility of the catalytic species in
toluene can obscure the electronic effects on the reaction.
TpCPCorrFeCl has been exploited to build up a metal–organic
framework (MOF) with the Zr6 cluster and was tested for the
catalysis of hetero Diels–Alder reactions between benzaldehydes
Fig. 43 The formation of heterocycles catalysed by Co–corrole anions.84 and dienes (Fig. 46).85

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Fig. 45 Molecular structures of Co corrole catalysts tested for hetero-
cycle formation.84
Fig. 46 Hetero Diels–Alder reactions between benzaldehydes and
dienes.85
It was necessary to treat the Zr-MOF-TpCPCorrFeCl with
AgBF4 to obtain (Zr-MOF-TpCPCorrFe)BF4, the active catalytic
species. Dihydropyran was obtained with an almost quantita-
tive 96% yield, significantly higher than that obtained with the
analogous homogeneous iron corrole complex. The scope of the
reaction was proved by the reaction of different substituted
benzaldehydes, obtaining in all cases the corresponding dihy-
dropyran in good yields, always higher than those of the
homogeneous catalysts. Both electronic and steric factors
influenced the reaction: while electron-donating benzaldehyde
substituents favored high yields, a significant reduction was
observed in the case of the sterically demanding tert-butyl
substituent.
(Zr-MOF-TpCPCorrFe)BF4 was stable under the reaction
conditions and it was recovered after the reaction and reused
for three cycles without a significant reduction of the yield.
Penta-coordinated phosphorus corroles have been exploited
as Lewis acids to catalyze different reactions.86 The complexes
have been synthesized following the pathway reported in
Fig. 47.
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Fig. 47 Synthetic routes to P corroles.86
These species were exploited to catalyze different reactions, such
as ketone hydrosilylation and deoxygenation using HSiEt3 as a
terminal reductant. The excellent results obtained led to the testing
of more challenging reactions, such as ring closure and the
deoxygenation of sugars. In all these reactions, the cationic P corrole
was stable and it was recovered intact at the end of the reaction.
CF3-Substituted TPFCorrPF2 were investigated as photocata-
lysts for the bromination of phenol with HBr.87 The presence of
CF3 substituents improves the oxidizing power of the related
complex, with the hypothesis that the increase of this oxidizing
power improves the efficiency of the photocatalyst. Following
this hypothesis, the performances of the P corroles reported in
Fig. 48 were compared with those of the gallium complex
because this corrole has the greatest oxidizing power in its
photoexcited state. The excitation was set at 400 or 450 nm but
in both cases, the (CF3)5TPFCorrPF2 was the most efficient, with
the highest TON, even at 450 nm where Ga corrole absorbs more.
The same superior activity was observed in the case of the
bromination of toluene and benzene, which produced benzyl
bromide and bromobenzene. These results indicated the ben-
eficial effects of CF3 substitution for the photocatalytic effi-
ciency of these P corroles.
This effect was confirmed in the case of analogous CF3-
substituted TPFCorr complexes of Al and Ga (Fig. 49).88
Also, in this case, the reaction investigated was the bromination
of phenol and toluene using HBr as the bromine source, formed
after the photooxidation catalysed by corrole complexes. Using a
400 nm LED for the photosensitization, a mixture of ortho- and
para-bromophenol was obtained. The catalysts were stable under
the reaction conditions and the best results were obtained with the
(CF3)3TPFCorrGa, almost in agreement with the order of the value
of the first oxidation potential, although (CF3)4TPFCorrGa was less
efficient; this variation was attributed to the different absorbance
of the two complexes at 400 nm.
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also investigated, using a LED at 600 nm and the best catalyst

(CF3)3TPFCorrGa. In this case, a reduced catalytic efficiency was
observed, with a significant reduction of TON, but no benzal-
dehyde was detected in these conditions.
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3. Solar cells
Although the remarkable photophysical properties of corroles
make them obvious candidates for application in organic solar
cells, only sparse examples of corrole-based devices have been
reported in the literature.
The first examples of such applications were reported for
dye-sensitized solar cells (DSSC) and the low efficiency obtained89,90
probably discouraged further studies in this direction. The reason
for these low efficiencies has been attributed to the scarce yield of
the electron injection process from corrole to TiO2.85
To investigate the possibility of circumventing this draw-
back by synthetic modifications, Ga and P corrole complexes
were exploited as chromophores in DSSCs.91 The corrole was
functionalized with a peripheral carboxyl group to graft the
complex onto the TiO2 surface; Ga and P have been chosen
as coordinated metals because they show high fluorescence
quantum yields but they have different oxidation potentials.
The P complex was fully chlorinated in the b-position to obtain
a further shift in the oxidation potential (Fig. 50).
Although the cell efficiencies were again low, the P complex
had the highest value (1.9%), followed by Ga and then by the
fully chlorinated P corrole, which showed a very low efficiency
(0.02%). The results obtained were explicated in terms of
electrochemical and spectroscopic data. While the Ga deriva-
tive has an oxidation potential too low to be reduced by the
redox mediator, the fully chlorinated P complex, on the other
hand, has an oxidation potential too high to allow the electron
injection into the TiO2 conduction band. This hypothesis was
Fig. 48 Molecular structures of CF3-substituted P corroles.87
supported by the variation of the electrolyte solution, which
induced changes in the potential of the TiO2 conduction band.

Fig. 49 Molecular structures of Al and Ga corrole photocatalysts.88

The complexes were also tested under the same reaction

conditions for the bromination of toluene, to give benzyl-
bromide with again (CF3)3TPFCorrGa as the best catalyst.
Benzaldehyde was obtained as a by-product of the reaction,
although with lower TON. The possibility to use the Q band
absorption for the photosensitization of these reactions was Fig. 50 Molecular structures of Ga and P corrole photosensitizers.91

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Fig. 51 Molecular structures of TpCPCorrAu and TmCPCorrAu tested as
photosensitizers in DSSC.92
By increasing Li+ concentration and lowering the concentration
of tert-butylpyridine, the conduction band assumes the poten-
tials are more positive, making the electron injection more
favored from the Cl8 P corrole and in fact, the efficiency of the
DSSC slightly increased.
Au complexes of corroles functionalized with carboxyl
groups on the peripheral phenyl substituents (Fig. 51) have
been tested as photosensitizers in DSSC.92
The corresponding corrole free-bases were also tested but
their efficiencies were very low, below 1%. TmCPCorrAu gave
the best efficiency (3.5%), much higher than that of TpCPCorrAu.
CV characterization of these corroles was carried out to
elucidate the results obtained, giving insights into the energy
levels for the corroles involved in these DSSCs. The oxidation
potentials of all the corroles indicated that the redox mediator
(I/I3) could reduce the oxidized corroles, and the singlet
excited states for both Au and free-base corroles were also over
the energy of the conduction band of TiO2, while the excited
triplet state of the Au corrole was slightly below the conduction
band of TiO2. Although free-base corroles have the character-
istics necessary to act as photosensitizers, the low efficiencies
observed are justified by low kinetics in the electron injection
into the conduction band of TiO2, which cannot allow it to
compete with the excitation decay, thus dropping the DSSC
efficiency. The higher efficiency showed by TmCPCorrAu was
attributed to a more efficient electron injection mechanism,
which can be allowed by the long-lived excited triplet state,
although there was the problem of the uphill energy process.
On the other hand, the higher efficiency of TmCPCorrAu than
the corresponding para-isomer can be reasonably attributed to
both a geometric factor, which favors the interaction with the
TiO2 surface, and to the energy consideration because the
carboxyl groups in the meta-positions have a greater electron-
withdrawing character than those in the para-positions, due to
the absence of conjugation with phenyl rings. This also opens
the way to the possible optimization of the photosensitizer
properties of Au corroles.
To further elucidate the results obtained, a detailed investi-
gation of the photosensitizer behavior of carboxyl-substituted
Au corrole complexes was conducted, comparing them with the
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corresponding ReO and OsN derivatives.93 XPS characterization
confirmed the previously proposed hypothesis that TmCPCor-
rAu has a stronger interaction with TiO2 than the corres-
ponding para-isomer, although in this case, the difference in
efficiencies reported was smaller.
However, TmCPCorrAu showed much greater power conver-
sion efficiency (PCE) than the corresponding ReO and OsN
complexes. Since the optical and electrochemical characteriza-
tion clearly indicated that the electron injection is possible
from the excited singlet state for all these complexes, the higher
PCE for TmCPCorrAu should be justified. Transient Absorption
Spectroscopy indicated that the intersystem crossing for the Au
corrole was much slower than that of the other complexes. As a
consequence, in the case of the Au corrole the electron injection
from the excited singlet state can more efficiently compete with
the intersystem crossing process, thus justifying the better
performances of TmCPCorrAu as photosensitizers.
Au corroles have been also exploited in bulk-heterojunction
organic solar cells (BHJSC). In these devices, excitons are
generated by photoexcitation and then they move to the
donor–acceptor interphase, where they dissociate to generate
the photocurrent. The process that limits the efficiency of these
devices is the short lifetimes and diffusion path of the excitons,
which rapidly decay in both radiative and non-radiative path-
ways before dissociation. For this reason, the possibility of
using complexes having long-lived triplet exciton states could
avoid these problems, leading to increased cell efficiencies.
Au corroles present these features and have been exploited
as electron donors in bulk-heterojunction organic solar cells
with C70 as the electron acceptor.94 The scheme of the cells is
reported in Fig. 52.
Three different Au corroles have been investigated (Fig. 53).
The structure of the cell was obtained by the vacuum
deposition of the Au corrole. TPCorrAu and TCF3PCorrAu
Fig. 52 Structures of the solar cells developed by (a) vacuum deposition,
(b) the solution process. Reproduced from ref. 94, with permission from
Wiley, Copyright 2014.
Fig. 53 Molecular structures of Au corroles.94
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Fig. 54 The structure of the BODIPY-CorrGa-based BHJSC. Reproduced

from ref. 95, with permission from American Chemical Society, Copyright
Fig. 56 The structure of the perovskite cell using TtBuPCorrCu as the
2018.
HTM. Adapted from ref. 96, with permission from Wiley, Copyright 2020.

showed the best efficiency, in the order of 3.3 and 3.9%, the
recombination, so improving both fundamental mechanisms
highest values for this kind of compound.
for the cell efficiency, i.e., the exciton generation and the
Because these complexes also present good solubility, the
consequent dissociation in free charge carriers.
development of solution-processed devices (Fig. 52b) using
Recently, a TtBuPCorrCu was exploited as the HTM in
TCF3PCorrAu as the dopant in the PTB7 and PC71BM electron
perovskite solar cells.96 In these devices the HTM has the
donor and electron acceptor polymeric species has been
important function of collecting holes from the perovskite
reported. In this device, the Au corrole can act as both the
and injecting them into the cathode, reducing the undesired
electron donor and sensitizer. The efficiency reached 6%, the
exciton recombination at the interfaces. The most used HTM is
best value reported for similar devices, confirming the promising
spiro-OMeTAD, which presents some drawbacks, such as high
characteristics of Au corroles.
cost and low charge mobility, making it necessary to have a
A BODIPY-CorrGa dyad has also been tested as an electron
doping process that is difficult to control and a source of the
donor in a small molecule BHJSC, together with PC71BM as the
irreproducible performance of the cell and its overall instability
electron acceptor (Fig. 54).95
and humidity sensitivity. Another important problem with
The structure of the corrole derivative is reported in Fig. 55.
spiro-OMeTAD is its thermal instability, with significant dete-
The integration of corrole and BODIPY dyes allows for better
rioration over 60 1C. For these reasons, the search for a better
coverage of the visible spectrum with large molar extinction
HTM is one of the problems to be solved for the potential
coefficients. The electrochemical characterization indicated
introduction of perovskite solar cells in the market.
that the HOMO and LUMO energy levels match well as electron
TtBuPCorrCu was applied as the HTM in a perovskite cell
donors with those of PC71BM as the electron acceptor. A BHJSC
having the structure reported in Fig. 56, and the performances
having the structure reported in Fig. 54 and prepared by casting
were compared with those of similar cells using Li-doped
corrole and PC71BM showed a PCE of 2.54%. This initial PCE
TtBuPCorrCu or spiro-OMeTAD.
value was significantly increased to 6.60% by the solvent
The PCE of the TtBuPCorrCu and Li-doped TtBuPCorrCu-
vapor annealing of the layer. It was demonstrated by a detailed
based cells were 13.11% and 16.49%, comparable with the
characterization that this treatment from one side improves the
19.57% obtained with spiro-OMeTAD. However, Cu corrole
morphology of the film and from the other reduces the charge
showed an impressive improvement in the thermal stability
of the cell because the cells kept at 85 1C in ambient air for 1000
hours maintained a PCE of 42.42% and 60.39% of the initial
value in the case of doped and undoped corrole, while that of
spyro-OMeTAD dropped to the 6.64% of the starting value. The
possibility to further improve the Cu corrole properties as HTM
by rational peripheral functionalization can open the way for
the exploitation of these macrocycles as optimized HTM for
improved perovskite solar cells.

4. An introduction to chemical sensors

and sensor arrays
Chemical sensors are devices that convert the information
about the chemical state, represented by the concentration of
Fig. 55 The molecular structure of the BODIPY-CorrGa dyad.95 a specific compound or the composition of a complex sample,

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into an analytically useful signal.97 Here, ‘‘analytically useful
signal’’ means any signal for which an adequate and standar-
dized metrology exists.
At the present stage of technical progress, electronics is the
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technology where signals can not only be measured but also
processed, stored, transmitted, used to activate automatic
processes, and presented to humans.98
The connection with electronics accommodates the design
of sensors as devices physically connected to electronic circuits
where signals (either analog or digital) carry information about the
analytes to which the sensors are sensitive. The parallel advances
in microelectronics and sensors are at the basis of the wide
pervasiveness of electronics systems in all aspects of technology.
The logical structure of sensors and the chain of transforma-
tions leading from the concentration of an analyte to the
corresponding electric signal are shown in Fig. 57. In this
scheme, the sensor itself is conceptually made by two main
elements: the sensitive material and the transducer.
The sensitive material is where the chemical interaction with
the analyte takes place. The interaction itself is not observable,
but the interaction changes one of the more measurable physical
quantities of the sensitive material. The transducer is a physical
sensor aimed at measuring one of these quantities.
The targets of chemical sensors are countless. Furthermore,
subtle differences in the chemical structures of analytes may
result in large variations in functionalities. The complexity of
the problem prompted the development of sensitive materials
of different natures, ranging from inorganic metal oxides to
polymers and molecular materials.
The chemistry of porphyrinoids is one of the most versatile
platforms for the design of sensitive materials.12 Several
Fig. 57 (A) A conceptual scheme of chemical sensors. Analytes interact
with the sensitive material, changing some of its physical properties (e.g.
the mass: Dm, the conductivity: Ds, the surface potential: DF; or the
absorbance spectrum (DAl). The transducer is a physical sensor sensitive
to one of the above-mentioned physical quantities, and, from the point of
view of electronics, it is a circuit element. Thus, the interaction with
analytes results in a change of resistance (DR), or capacitance (DC), or
transconductance (Dgm) or the frequency of a resonator (Df). In the
interface circuit, the transducer response is converted into a measurable
electric signal in the domains of time and frequency (Dv(t, f)). An example
of the transforms chain is shown in panel B. A material made of corrole
receptor molecules is applied to coat the surface of a mass transducer.
The transducer is an electromechanical resonator that forces the signal of
an oscillator circuit to its own resonance frequency. A frequency meter is
then applied to measure, at a given temporal rate, the circuit output. A
time-variable signal manifests the adsorption of molecules onto the film of
corroles.
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properties of these molecules can be used to manifest the
interactions with host molecules: for example, they are natural
chromophores, are characterized by large p-aromatic systems
and they are versatile chelating frameworks that can reversibly
bind with environmental molecules; target analytes can also
mediate both photophysical and/or redox processes.
Porphyrins have been the most frequently used porphyrinoids
for sensor development. However, corroles, even though less
utilized so far, are attracting significant interest because,
besides sharing most of the properties of porphyrins, they are
characterized by enhanced features that make them appealing
for chemical sensors development.
The characteristics of corroles make them eligible to be used
with several transducers, giving rise to several different kinds of
chemical sensors for analytes dispersed in air and in solution.
In general, the consequence of interactions with analytes
affects multiple physical quantities; therefore, the same corroles
can be used with more transducers. This versatility is particularly
important for chemical sensor arrays made by ensembles of
sensors of different properties.
The topic of porphyrinoids-based sensors has been recently
reviewed with privileged attention to porphyrins.12 In this
review, the focus is on the applications of corroles as chemical
sensors. The discussion is organized from the point of view of
the transducers and it is introduced by an illustration of the
basic features of chemical sensors and sensor arrays.
The field of sensors is extremely large, involving devices
dedicated to the measurement of a large number of physical,
chemical, and biological quantities.99 In spite of such a vast
number of devices and purposes, the definition of chemical
sensors given above can be extended to any kind of sensor. In
particular, all sensors, disregarding the nature of the measured
quantity, are electronic devices. Thus, the properties of sensors
can be represented by a set of universal quantities that standardize
the communication of the sensor performance and properties, and
enable comparison among different devices.100
An important property of sensors is the capability to detect a
target analyte when this is presented in a mixture with other
compounds. This property is called selectivity and in a selective
sensor, the sensitivity to the target compound prevails over all
the others.
The large number and variety of chemical compounds make
it difficult to design selective sensors. More practically, sensors
can be designed with a dominant sensitivity to particular
molecular motifs that can be found in different molecules.
Corroles are a typical case of a receptor capable of multiple
interactions. Molecular design can emphasize one interaction over
the others but the selectivity may remain limited. Non-selective
sensors produce ambiguous signals, and samples made by differ-
ent mixtures of compounds can result in very similar signals. So,
the use of non-selective sensors is restricted only to those cases
where the chemical complexity is limited and the compounds
are known.
However, a lack of selectivity is typical of the olfactory
neurons found in olfaction, which is the gas analyzer of
animals.101
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The noteworthy feature of such a system is that with a
limited number of receptors, a large number of different
olfactory stimuli (what we called odors) can be detected. It
has been estimated that humans can detect more than trillions
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of different stimuli.102 Such a performance is achieved by the
combinatorial selectivity of the receptors.103 In practice, each
receptor is sensitive to more molecules and the same molecule
may be sensed by many receptors.
The lack of selectivity of chemical sensors and olfactory
receptors establishes a link between these very different kinds
of ‘‘devices’’, which gives rise to artificial olfaction systems.104
The term electronic nose has been reserved for systems based on
arrays of sensors aimed at analyzing gaseous samples. However,
the above description of olfaction is also valid for aquatic animals
such as fish and amphibians. The application of the principle of
the electronic nose to sensors for compounds in solution is a
later development of artificial olfaction systems and arrays of
sensors for solutions are usually called electronic tongues.105
Electronic noses and tongues are made by two major com-
ponents: the sensor array and the data analysis.106 The sensor
array reproduces the olfactory receptors neurons and it is
formed by an ensemble of chemical sensors that are unselective
but characterized by different sensitivity profiles. Data analysis is
the analog of olfaction processing that starts in the olfactory bulb
and ends in the brain where stimuli are identified and memor-
ized. Sensor arrays produce multivariate data that need to be
treated with proper multivariate data analysis techniques.107
The algorithms to treat these data are studied by chemo-
metrics, which is diffused beyond analytical chemistry. Algo-
rithms such as the principal component analysis (PCA) for the
representation of multidimensional data are popular even to a
general audience.108
The design of efficient sensor arrays requires the control of
the sensitivity profile of individual sensor elements in order to
emphasize the detection of a relevant category of compounds.
From this point of view, the wide synthetic flexibility of
corroles provides a unique opportunity for the development of
sensor arrays.
4.1 Optical sensors
In optical sensors, the interaction with the analyte is manifested by
the changes in the optical properties of a sensitive material. The
term optical properties indicate the modality of interaction
between the electromagnetic radiation in the visible range and
the material. These include both absorption and emission spectra.
Standard optical sensor arrangement is based on the illu-
mination of the sensitive material with a light source and in the
detection of light transmitted, or reflected or emitted by the
material. Transmitted and reflected light are expressions of the
absorption properties, while emitted light is generated as
secondary emission in photoluminescence phenomena.
Although the measurement setup is, in principle, simple, the
quality of the analytical signals depends on several factors that
require the careful design of the sensor. First of all, the choice
of the light source is fundamental to capturing the relevant
changes in the sensitive materials. Light sources characterized
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by a continuous spectrum should be preferred because they do
not exclude any wavelength. Examples of continuous sources
are the black body radiation emitted by incandescent bodies,
such as tungsten bulb lamps. These lamps are typically used in
desktop spectrophotometers but are not suitable for portable
devices. A widely used alternative is the use of LEDs.109 These
are miniaturized semiconductor devices that can emit a large
amount of radiating power. However, the spectral intensity of
LED light is non-homogeneous. White LED that should cover
the whole range of visible light is characterized by a lack of
intensity between the blue and green regions of the spectrum.
Thus, the use of LEDs requires a careful analysis of the
wavelength range of interest by the interaction with the analyte.
The detection of light is usually performed by silicon photo-
diodes that ensure good responsivity in the visible range. The
responsivity of silicon detectors grows almost linearly with the
wavelength, then they are more sensitive to red as compared to
blue light where the Soret band occurs.110
The growth in the performance of consumer optoelectronics
devices prompted the development of low-cost advanced opti-
cal equipment such as digital scanners and cameras embedded
in ubiquitous devices such as computers, tablets, and
smartphones.111 The optical sensitivity of these devices largely
fits the requirements necessary to capture the optical changes
occurring in sensitive layers. In silicon detectors, the optical
spectra are decoded in three values approximating the human
eye spectral response (RGB). The algorithm of codification is
not unique and alternatives to the use of more efficient color
codes have been suggested for analytical purposes.112
Optical sensors require that the receptors are either immobi-
lized on a solid substrate or dissolved in a solution. In both cases,
is important to consider that the detector receives the light from
an angle of view, thus the geometry of the sensor arrangement has
to be optimized in order to collect light as much as possible.
The immobilization in a solid phase requires that the
sensitive receptors are absorbed, covalently or ionically, or
simply encapsulated into a solid matrix that is permeable to
the analyte and transparent to the light.
4.1.1 Oxygen sensors. 5,15-Bis(pentafluorophenyl)-10-(4-
methylphenyl)-corrole has been investigated as oxygen sensor.113
This corrole undergoes photobleaching under vacuum, while in
the presence of molecular oxygen a significant increase of fluores-
cence emission is observed. This result suggests that light induces
a prompt formation of a strongly emissive species from corrole in
the presence of oxygen, which can be exploited for gas detection.
Oxygen sensing properties of corroles are improved when
used in combination with quantum dots. An example is provided
by self-assembling and micelle encapsulated quantum dots.120 In
this example a fluorescent semiconductor CdSe/ZnO core–shell
was coated by a self-assembled layer of a Au(III) corrole endowed
with a carboxylic acid moiety to promote surface binding.
The signal transduction in this system is based on the
Förster Resonance Energy Transfer (FRET) where energy is trans-
ferred from the quantum dot to the corrole via a long-range
dipole–dipole interaction. As a result, the emission energy of the
quantum dot is decreased. Fig. 62 shows the sensor elements
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with and without the micelle encapsulation. The quenching of

the triplet state by molecular oxygen is related to the molecular
oxygen concentration by the Stern–Volmer equation:
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t0
¼ 1 þ kq  ½ O 2 
t

where t0 and t are the radiative lifetimes of corrole without and

in the presence of oxygen, kq is the quenching rate constant and
[O2] is the molecular oxygen concentration. The results show that
micelle encapsulation is a viable method for exploiting FRET
signal transduction (Fig. 58).
This study was aimed at monitoring and imaging tumor
microenvironment which are found in hypoxia conditions,114
with a concentration of oxygen below 5 torr.
4.1.2 Anion sensors. The detection of anions is of great
importance in many contexts. For instance, anions are present
in many biological systems; DNA is a polyanion and most of the
enzymes and co-factors are anionic. Furthermore, pollutant Fig. 59 Scheme of the 3-substituted TPFCorrGa complex (panel A) and
anions are supposed to be related to the eutrophication of spectrofluorimetric titration of F (panel B), CN (panel C), and H2PO4
rivers (from the over use of phosphate-containing fertilizers) (panel C) in toluene. The insets of panels B, C and D show the response
and carcinogenesis (metabolites of nitrate).116 curves of emission intensity at 616 nm to the concentration of the three
compounds in units of 105 M. Adapted from ref. 117, with permission from
The fluorescence of 3-substituted TPFCorrGa complexes is
Elsevier, Copyright 2014.
found to be modulated by the concentration of various anions,
such as spherical halides (F, Cl, Br, and I), linear anions
CN,117 bulky anions (such as CH3COO and H2PO4), and basic conditions, suggesting the formation of two distinct species
amines such as caffeine and nicotine,118 see example in Fig. 59. due to the protonation and deprotonation of the 8-hydroxy-
These systems were prepared in solid-state membranes using quinoline moiety (see Fig. 60). This twofold phenomenon gave
polyacrylamide and polymethylmethacrylate. rise to the symmetric detection of acidic and basic conditions.
The functionalization of the same Ga complex with cou-
marin increased the solubility of the compound and enabled 4.1.2.1 Fluorides. Silicon is one of the last complexes of
the detection of various anions such as cyanide and fluoride at corrole to be synthesized. The preparation of Si–corrole is
the sub-ppm detection limit.119 similar to those leading to homologue complexes containing
The functionalization of Ga-corrole with an 8-hydroxyquinoline germanium or tin.
moiety resulted in a pH-sensitive fluorescent dye.120 The intensity
of the emission, excited at 500 nm, decreased both in acidic and

Fig. 58 Corrole-based quantum dots as oxygen sensors. Panel A shows

the structures of the two corroles. Panel B shows the self-assembly of
corroles onto the surface of a fluorescent nanoparticle and the direction of
FRET charge transfer. Functionalized quantum dots are then encapsulated
in micelles. Panel C shows the changes in the fluorescence decay. A
Stern–Volmer plot of compound 1 calculated with intensity and lifetime
decreases. Reproduced from ref. 115, with permission from Royal Society
of Chemistry, Copyright 2015.
Fig. 60 (A) 8-Hydroxyquinoline Ga(III)corrole. (B) Proposed mechanisms
of photoinduced electron transfer (PET) from 8-hydroxyquinoline and
corrole in the three states, consequent to the exposure to acid and basic
conditions. (C) Emission spectra as a function of pH in acidic and basic
solutions. Reproduced from ref. 120, with permission from the Royal
Society of Chemistry, Copyright 2019.

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In terms of chemical sensitivity, the large energy of the Si–F
bond suggests that Si–corrole may work as a fluoride sensor.
Fluoride ions are hard Lewis bases, with a small ionic radius
and large charge density. These unique properties of fluoride
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ions make it an interesting target for sensor design for its
involvement in different technological, medical, and biological
processes. Fluoride is an essential anion in humans where it is
known to prevent dental caries.121 On the other hand, fluoride
consumption at high levels is associated with conditions such
as nephrotoxic changes and urolithiasis.122
The interactions with F result in changes in both absorbance
and fluorescence with high selectivity as compared to other
anionic species.123 Fig. 61 shows the color comparison of SiIV
triarylcorrole in a DMSO/H2O) solution with 105 M of different
anions. The distinct response to F is preserved by Si–corrole
spotted on paper and immersed in a buffered aqueous solution.
To improve the performance of the optical F sensor,
Si–corrole was embedded in highly lipophilic polyvinylidene
fluoride (PVDF) nanofiber mats.124 The lipophilic layer is
expected to improve the sensitivity, favoring the contact between
the sensitive dye and the aqueous sample and improving the
sensor stability. TTCorrSiOH was blended with PVDF fibers and
the fluorescence was measured in a microplate. Emission inten-
sity at either 590 nm or 635 nm showed sensitivity down to 105
M of fluoride in MES-buffered water.
Fig. 61 (A) Fluoride-sensitive TTCorrSi. (B) Absorbance spectra at various
concentrations of F in DMSO. (C) Colorimetric comparison of the addi-
tion of different anions in DMSO. The cuvette labeled as L shows the
pristine solution. (D) Colorimetric changes in Si(IV) corrole immobilized in a
paper strip at different concentrations of F in MES buffer at pH = 5.5:
(a) = 102 M L1; (b) = 103 M L1; (c) = 104 M L1; (d) = 105 M L1;
(e) = 106 M L1; (f) = blank solution. Reproduced from ref. 123, with
permission from Wiley, Copyright 2018.
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Fig. 62 (A) A schematic representation of a fluoride-sensitive corrole.
(B) The spectrofluorometric titration of F in toluene. The inset shows the
emission intensities at 626 nm and 680 nm with respect to the concen-
tration of F in units of 105 M. (C) Spectrofluorometric titration of F for
the compound in scheme A immobilized in polyacrylamide. The insets
show the dynamic response versus time for the emission at 624 and
680 nm. Adapted from ref. 118, with permission from the Royal Society of
Chemistry, Copyright 2012.
Good sensitivity and selectivity to fluoride were also exhib-
ited by free-base trans-A2B-corroles, where A is a nitrophenyl
and B is either pentafluorophenyl, 2,6-difluoro, 3,4,5-trifluoro,
or a 4-carboxymethylphenyl group.125 The immobilization of
TPFCorrH3 in polymethylmethacrylate (PMMA) and polyacryla-
mide has been shown to retain the sensitivity to fluoride (see
Fig. 62).118
Another example of anion sensors showed a free-base bis-
pyridylcorrole whose fluorescence emission was found to be
turned on in the presence of ZnII. Studies in solution showed a
1 : 1 binding mode of Zn–ClO4 in the pocket of the free-base
molecule.126
4.1.2.2 Cyanide. Cyanide is known to be one of the most
poisonous anions. Its poisoning effect is due to the binding of
iron in cytochrome c oxidase that interferes with charge trans-
fer and results in general hypoxia.
The cyanide sensitivity of a derivative of the 3-substituted-
TPFCorrGa complex was demonstrated in solution.117 In the
presence of cyanide, a decrease in emission intensity and a red
shift in the emitted light were observed. The intensity of
emission at a fixed wavelength (616 and 618 nm) measured
with a desktop spectrofluorometer provided a limit of detection
of 0.33 mM.
Selective cyanide detection was demonstrated by TTCorrCo(PPh3)
spotted on paper and imaged by a standard smartphone (Fig. 63).127
The corrole dissolved in THF was spotted onto a Whatman 1003-110
filter paper. Results enabled the detection of cyanide below 104 M
in real samples such as tap water and the saliva of smoker and non-
smoker subjects.
4.1.2.3 Iodide. Among the anions, iodide is an essential
element due to its role in several physiological activities such
as brain function and cell metabolism, and it is related to
thyroid function.128 An electron-deficient Br8TPFCorrCu (B)
was found to be a highly selective colorimetric sensor for iodide
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Fig. 63 (A) A schematic representation of the CN-sensitive
TTCorrCo(PPh3). (B) Images taken with a smartphone in ambient light, at
a color temperature of 4780 K, of the TTCorrCo(PPh3) in scheme A spotted
in filter paper and exposed to a 0.01 M concentration of anions in water.
Adapted from ref. 127, with permission from World Scientific, Copyright
2020.
129
(see Fig. 64). The compound showed a colorimetric response
to increasing iodide concentration with a decrease in the
absorbance peak at 424 nm, and an increase in absorbance at
441 nm. The feature at 441 nm is also very selective as
compared to other anions.
4.1.3 Heavy metal ions. Covalent organic frameworks are
porous crystalline polymers endowed with tunable high porosity
and low density, and these properties make them interesting in
several applications.130,131 A corrole-based covalent organic
framework was found to be sensitive to several metal ions
(Fig. 65), in particular, Ga(III), Al(III), Cr(III), and Fe(III).132 The
exposure to metal ions enhances the fluorescence properties,
Fig. 64 (A) The molecular structure of the iodide-sensitive Br8TPFCorrCu.
(B) The sensitivity to I can be explained by considering the one-electron
oxidation of iodide by the highly electron-deficient Cu(II) center; the
bromine atoms facilitate strong electron-withdrawing effects, resulting
in the color change of the Cu–corrole complex. (C) The above-described
process is highly selective to iodide as compared to other anions, as shown
by the absorbance at 441 nm. Reproduced from ref. 120, with permission
from the Royal Society of Chemistry, Copyright 2019.
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Fig. 65 (A) Schematic representation of mercury-sensitive corrole. (B)
Emission fluorescence at increasing concentrations of Hg2+ in toluene
upon the addition of methanolic solutions of Hg(II)–acetate. Fluorescence
excited at 450 nm. (C) A Stern–Volmer plot showing a limit of detection
around 7 mM. (D) Comparison of the fluorescence quenching for various
cations at 2  106 M in toluene. Reproduced from ref. 135, with
permission from Royal Society of Chemistry, Copyright 2012.
except in the case of Cu(II), which instead quenches the emis-
sion of light.
Mercury is one of the most toxic elements in nature.
Inorganic mercury toxicity is found at concentrations of the
order of 5 mg L1.133 The sensitivity of corroles to mercury has
been studied by two research groups. In the first paper, the
sensitive properties of a membrane made of TPFCorrH3 were
investigated.134
Corrole was mixed with poly(vinyl chloride) and dioctyl
sebacate as plasticizers, and tested with respect to Hg2+. Results
showed a linear response with the logarithm of the concen-
tration of Hg2+ in the range 107–104 M. In comparison to a
similar sensor made with TPPH2, the sensor exhibited a wider
range of linearity and a shorter response time.
Another paper (see Fig. 68) studied additional donor–accep-
tor A2B-corrole systems where A was nitrophenyl, and N,N-
dimethylaminophenyl, thienyl, naphthyl and tridecyloxyphenyl
groups were compared as the B group.135 For the system
functionalized with tridecyloxyphenyl, the Stern–Volmer plot
is linear down to 108 M (see Fig. 66) and the system is highly
selective to various cations.
4.2 Electrochemical sensors
Chemical sensors based on electrochemical processes have
been in use for more than a century. Electrochemistry was
developed for electric power production and storage and soon
showed its potential for the detection of compounds. Usually,
the realm of application of electrochemistry is the detection of
compounds in electrolytic solution. However, several examples
of sensors based on solid-state ionic conductors are also
available.
Electrochemistry manifests the interaction at the solid–
liquid interface between the sensor surface and the compound
in solution. Electrochemical sensors are grouped into two main
categories, namely, those working in equilibrium and those in
non-equilibrium conditions. In the first category, the equilibrium
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Fig. 66 (A) A schematic diagram of the solvothermal synthesis of a
corrole-based covalent organic framework. (B) Vertical and lateral views
of the stacking mode. (C) Absorbance and emission spectra. (D) A com-
parison of the emission intensity at 635 nm, excited at 425 nm, of
0.1 mg mL1 solution of the compound in scheme A in THF. Ions were
added at 2  104 M. The intensity was normalized in the blank solution.
The emission was enhanced by Ga(III), Al(III), Cr(III), and Fe(III) and quenched
by Cu(II). Reproduced from ref. 132, with permission from American
Chemical Society, Copyright 2020.
of the electrochemical potentials of species in solid and solution
leads to an electrode potential proportional to the concentration
of the analyte in solution. These sensors are called potentiometric
sensors and they are based on the measurement of the electrode
potential with respect to a constant reference potential. In the
second approach, the equilibrium is altered by an applied
potential that can lead to redox reactions at the electrode surface
with the consequent release of electrons in the solid and ions in
the solution. This second approach is amperometric and it is
based on the measurement of current at known applied
potentials. Also, in this case, the application of the potential to
the electrode needs a potential reference, which is provided by
the reference electrode.
Both approaches require a specific electronic circuit at
which sensitive and reference electrodes are connected. In
potentiometric measurements, in order to maintain the equili-
brium, no current has to flow at the electrode–solution inter-
face. This condition is ensured by high-input impedance
operational amplifiers. In amperometric measurements, the
potential of the reference electrode does not have to be altered
by current, thus the current flows from the sensitive electrode
(working electrode) and an auxiliary electrode (counter-
electrode). The three-electrode configuration is provided by a
circuit, called a potentiostat, that enables the measurement of
current at variable voltages in the so-called voltamperometric
modality.
The continuous miniaturization of integrated electronic cir-
cuits led to the design of a single-chip potentiostat that greatly
increased the miniaturization of electrochemical sensors.136
4.2.1 Cations. A highly selective sensor for Ag+ was devel-
oped by preparing a membrane containing TPFCorrH3 as the
electroactive component, 2-nitrophenyl octyl ether (o-NPOE) as
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a plasticizer and the additive sodium tetraphenylborate
(NaTPB).137 The response of the electrode was found to be
Nernstian down to 105 M and selective toward a large number
of mono-, bi- and tri-valent cations.
An original combination of porphyrins and corroles in the
same electrode was demonstrated for the detection of K+. The
two macrocycles carried the same metal atom but in different
oxidation states.138 In particular, TtBuPPCo(II) and TtBuPCorr-
Co(III) were used to prepare a membrane containing sodium
tetrakis-[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB) vali-
nomycin, 64.3% bis(2-ethylhexyl sebacate) (DOS), and 31.7%
poly(vinyl chloride) (PVC).
The couple of porphyrinoids carrying cobalt at different
oxidation states is expected to improve the stability of the
potential. This is usually obtained by adding a redox reagent
to the sensor formulation. In this approach, the redox potential
is stabilized thanks to the formation of two independent
irreversible redox systems, resulting in mixed potential for-
mation. This concept was tested with respect to potassium ions
by adding valinomycin, a well-known potassium-selective iono-
phore, as the ion-selective element in the sensor membrane
composition. A similar method was previously exploited to
prepare a fluorescent potassium sensor.139
The same system has been demonstrated on a disposable
support such as paper (see Fig. 67); the ion-selective electrode is
made by coating the paper with a carbon nanotube layer.140
4.2.2 Anions. Corrole-based electrodes are sensitive to pH,
such as in the acidic conditions of salicylic acid.141 The
sensitivity to salicylic acid is improved by the addition of a
cationic lipophilic salt such as tridodecylmethylammonium
chloride, reaching a limit of detection of mM at pH below 4.5.
4.2.2.1 Nitrite and nitrate and nitric oxide. TTCorrCo has a
binding affinity for nitrate and nitrite. In order to exploit this
preferential binding, the corrole was embedded in a PVC
plasticizer membrane and the binding of nitrite was detected
via potentiometric measurement.142 The response is Nernstian
with a constant slope above 106 M of NO2 in a phosphate
buffer solution kept at pH 4.5. The detection is reversible so it
Fig. 67 (A) A schematic representation of the construction of a paper-
based ion-selective sensor incorporating valinomycin as a potassium
chelating element, and a mixture of Co(II) and Co(III) complexes of
porphyrin and corrole in multiwalled carbon nanotubes. (B) The potentio-
metric response of the sensor versus the activity of K+. Electrodes were
prepared with a 1 : 1 porphyrin/corrole ratio and for different cation
exchangers (KTFB: potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]-
borate and NaTFBP: sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]-
borate) and without multiwalled carbon nanotubes (MWCNT). Adapted
from ref. 140, with permission from Elsevier, Copyright 2018.
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can be used for continuous monitoring. Selectivity depends on
the formulation of the membrane and thus on the choice of
plasticizer and ion exchanger. For instance, tributylphosphate
and tridodecyl methyl ammonium chloride (TDMACl) were
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found to increase the selectivity toward nitrate.
4.3 Resistive sensors
Resistors are the simplest electronic components, and their
integration into electronic systems is the easiest. Thus, resistive
sensors are available for very different quantities such as
temperature, light, magnetic field, and mechanical strain.99
The fabrication of resistive sensors requires the deposition
of the sensitive material onto an insulating substrate, in order
to segregate the resistivity of sensors from other influences. The
measure of resistance needs the presence of a couple of metal
electrodes, typically made of gold. Electrodes are either depos-
ited directly onto the substrate or on top of the sensitive
material. The first case is more diffused because it allows the
application of the sensitive material as the last step of sensor
fabrication, avoiding any chemical contamination due to post-
processing. The relationship between the conductivity of the
sensitive material, which is the quantity affected by the inter-
action with the analyte, and the measured resistance depends
on the geometry of electrodes and the distance between the
electrodes. Since organic materials are usually scarcely con-
ductive, electrodes are shaped in the form of an interdigitated
pair of electrodes. The number of pairs and the distance
between the electrodes can be adjusted in order to set the
resistance in the MO range. This is obtained with a micrometer
gap between the pair of electrodes. The relationship between
geometry, conductivity, and resistance can be evaluated by
proper geometric transform.143
Chemically sensitive resistors made of metal–oxide semi-
conductors, such as SnO2, have been the most diffused gas
sensors in the last few decades.144 Their compatibility with
microelectronic processes makes the integration of gas sensors
in microsystems possible.145 In spite of these qualities, these
sensors need to be operated at temperatures above 200 1C, thus
requiring a non-negligible power. Furthermore, these sensors
are scarcely selective and poorly flexible in terms of selectivity
design. For these reasons, there has been a strong effort
devoted to the design of organically conductive materials such
as conductive polymers146 and conductive molecular films like
phthalocyanines.147
The conductivity of corrole films is sometimes remarkable,
as shown by their use as charge carriers in solar cells.96
However, the full potential of sensors based on conductive
corrole films has not yet been exploited.
The affinity of corrole for nitric oxides promoted the inves-
tigation of gas sensors for the detection of NO2. This gas is a
major pollutant in urban areas and is mainly produced by
natural and anthropogenic processes. The long exposure to
NO2 is correlated with several diseases of the respiratory
tract,148 and it is correlated with the most severe consequences
of COVID-19.149 NO2 can be detected with high sensitivity
by using chemiluminescent methods.150 The development of
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low-cost detectors has been mostly based on metal oxide
semiconductors that, in spite of good sensitivity, are non-
selective and need to be operated at high temperatures. Corroles
are good candidates for the detection of NO2 but in order to
prepare a sensor, it is necessary to arrange the corrole molecules
in a conductive solid-state material.
A self-arranged semiconducting nanostructure was developed
with 10-HDPCorrH3 and TpMCPCorrH3.151 These molecules self-
arrange in nanoneedles and nanoribbons, respectively. The
aggregates of nanostructures show an ohmic conductivity that
is greatly affected by the exposure to NO. Both the molecules
show an n-type response to NO2 at room temperature, where the
gas adsorption results in a decrease in conductivity with a limit of
detection smaller than 100 ppb.
In general, resistive corrole sensors are used in donor–
acceptor composites. Carbon-based materials, such as CNTs,
are excellent electron acceptors that can be functionalized with
donor species.152 A gas sensor example of this approach has
been provided with TTCorrH3 non-covalently linked to single-
wall carbon nanotubes.153 CNTs are p-type conductors, thus the
injection of electrons from corroles depletes the CNTs of charge
carriers with the consequent reduction of conductivity. The
exposure to NO2 increases the conductivity of the sensor
(Fig. 68). This effect can be explained considering that the
acceptor character of NO2 drags electrons from the corrole and
thus it results in the depletion of charge carriers in the CNT.
The sensor has been demonstrated to detect NO2 below 50 ppb.
An alternative carbon-based composite material was pre-
pared with reduced graphene oxide. The presence of carboxyl
and hydroxyl functional groups on the graphene oxide makes
the structure suitable for the formation of organic frameworks
incorporating macrocycles. The concept was applied to trans-
A2B-type corroles such as 10-(4-chlorophenyl)-5,15-di(4-methyl-
phenyl)-corrole and its cobalt complex154 and resulted in a sub-ppm
detection limit of NO2.
A further approach to resistive chemical sensors was based
on donor–acceptor couples where the electron transfer is
Fig. 68 (A) A schematic representation of the Cu–corrole complexes
sensitive to NO2. (B) Scanning electron microscopy image of the self-
assembled nanostructures formed by compounds in scheme A. (C) The
current–voltage curves of nanoneedles (1) and nanoribbons (2). (D) The
sensor response curves fitted with a quadratic curve shows the greatest
sensitivity of the nanoribbons (compound 2) as compared to the
nanoneedles. Reproduced from ref. 151, with permission from Elsevier,
Copyright 2019.
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promoted by light. These structures have been widely investi-
gated and exploited in the so-called dye-sensitized solar cells
whose heart is the interface between an organic dye and a wide
bandgap semiconductor.155 Among the organic dyes, the
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combination of porphyrins and nanostructured titanium oxide
achieved the best performance.156 The central mechanism of
the dye-sensitized solar cell results in a photoconductive sensor
where the illumination with visible light (captured by the
organic dye) induces a change in the conductivity of the
semiconductor.
A few years ago, this mechanism was also exploited for
chemical sensors. The charge transfer induced by light may
also occur because of a charge transfer from an adsorbed
molecule to the dye. Additionally, under illumination, the dye
is depleted of electrons and the charge transfer from a donor
adsorbed molecule becomes more probable. This concept was
first demonstrated with porphyrins-coated zinc oxide nanorods
and it resulted in conductive sensors where, under visible light,
the sensitivity towards donor species (such as triethylamine) is
strongly increased.157
The similarities between corroles and porphyrins suggested
the development of light-activated gas sensors made of corrole-
coated ZnO nanoparticles.158 A one-pot fabrication procedure
was prepared where corrole was added to the precursor of
the ZnO hydrothermal synthesis precursor (see Fig. 69). The
reaction produced nanometric particles coated with a corrole
layer. These sensors, tested with a large range of volatile
compounds, showed a bimodal response. The resistance
decreased when exposed to donor species such as triethylamine
and triethylphosphite and increased under the exposure to
alcohols, alkanes, aldehydes, among others.
To interpret this behavior, it is necessary to consider that the
sensing material is made by an aggregate of organic-coated
nanoparticles and the molecular adsorption occurs at the
Fig. 69 (A) A schematic representation of the steps for the preparation of
corrole-coated ZnO nanoparticles. Corroles were added to a solution of
zinc acetate dihydrate and ethanol and kept at 120 1C for 12 h. The solution
was centrifuged and dried and the powder dissolved in toluene and used
as a coating by drop-casting on a glass substrate endowed with gold
interdigitated electrodes. (B) Transmission electron microscopy image
showing that the nanoparticles have a nonmetric size and a round shape;
the surface organic layer is visible in the pictures. (C) The sensor’s
sensitivity pattern shows the ambipolar response: electron donor species
decrease the resistance (negative sensitivity), while most of the other
compounds increase the resistance (positive sensitivity). Reproduced from
ref. 158, with permission from American Chemical Society, Copyright
2021.
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organic surface layer. Changes in current should be expected
in cases where the organic layer is either charged or polar.
However, also in the case of an electrically inert organic layer,
the adsorbed molecules might increase the separation between
nanoparticles, thus reducing the current.
It is important to consider that in a structured molecule,
such as a corrole, several interaction mechanisms are simulta-
neously active. Hydrogen bonds and van der Waals forces are
among the most effective with respect to volatile organic
compounds. Even if the largest sensitivity is observed for
electron donors, any other molecule can be adsorbed and
contribute to the sensor signal. Furthermore, compounds for
which the sensitivity is small can occur at large concentrations,
thus hindering the sensitivity towards the most sensitive species.
In papers where sensors are tested only towards the dominant
interaction mechanism, it is difficult to foresee the behavior with
real samples.
The behaviors of corrole-based sensors were compared with
those of porphyrin-based sensors.158 In particular, the sensitivities
of free-base macrocycles and copper complexes of TPPH2 and
TPCorrH3 were compared. Compared to porphyrins, the corrole
cavity is characterized by an additional hydrogen atom that leads
to a non-planar structure and a larger acidity, increasing hydrogen
bond affinity, which favors the ligand as compared to alcohols and
bases.159 In copper complexes, axial coordination tends to attenu-
ate the differences. In both macrocycles, copper is in the same
oxidation state; however, the electron-rich nature of corrole leads
to a ligand-to-metal electron transfer that transforms the macro-
cycle into a cation radical. As a consequence, the facilitated
reduction of copper corrole contributes to a larger sensitivity to
donor ligands.
4.4 Mass sensors
The measurement of mass is a straightforward approach to
detecting sorption interactions in a sensitive material.160 The
implementation of this concept requires a sensor that can
detect small mass increases due to the binding of airborne
molecules. High-sensitivity devices are based on mechanic
resonators where the resonance frequency is inversely propor-
tional to the mass. Simple kinematics considerations have
demonstrated that in these sensors, the sensitivity is propor-
tional to the resonance frequency. High-frequency resonators
are therefore necessary to achieve suitable sensitivities for
detecting the binding of molecules.161 The highest mechanical
resonance frequencies are found in crystals where the oscillation
modes can reach frequencies in the GHz range.162 However, such
large frequencies correspond to displacements at the atomic scale,
which are not directly observable. Piezoelectric crystals are a
noteworthy exception (e.g. quartz) where mechanical resonance
is naturally associated with electric resonance.163,164 These materi-
als, although very good electric insulators, are characterized by the
equivalent circuit of a resonant circuit. Thus, when they are placed
in oscillator circuits, voltage and current are driven by the mechan-
ical resonance of the crystal. Usually, quartz crystals are used in
this scope; when these crystals are used to measure mass, they are
called quartz crystal microbalances (QMBs).
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The first example of a corrole-based quartz microbalance sensor
was given with a Langmuir–Blodgett film of DMHECorrMn.165 The
characterization of the sensor showed the multiple interactions of
corrole that can simultaneously interact with a wide spectrum of
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SBA-15 type.168 More recently cobalt corroles were embedded in a
porous organic polymer in order to make the high surface area and
the porosity size suitable for the sorption of gases such as carbon
monoxide.169 The material retains the same sensitivity and selec-

interaction mechanisms, from coordination, to van der Waals
forces, and hydrogen bonds. Mass sensors do not select any of
these interactions so the sensor was found to be sensitive to
aromatics, aldehydes, alkanes, alcohols, and amines. However, the
nature of the interaction can be revealed by the adsorption iso-
therm, which can be described as a linear combination of each
interaction mechanism. Each interaction can then be described by
Langmuir isotherms and the difference between isotherms is given
by the affinity constant.
According to the affinity between the volatile compound and
the sensitive molecule, some interactions become saturated
before others, while in cases where the affinity is low, the
isotherm is practically linear and it follows Henry’s law of
sorption from the gas to the liquid phase. In practice, the
sensitivity of the sensor is greater at low concentrations and it
decays as the concentration increases.
Similar behavior was found by considering the adsorption of
gases on solid-state films of various Co(III) corroles. In these
materials, the adsorption isotherm of carbon monoxide was
compared with those of oxygen and nitrogen.166
The capability of selectively absorbing carbon monoxide as
compared to other gases was preserved in sol–gel formulations167
and incorporating the corroles in meso-structured silica of the
tivity toward carbon monoxide, indicating that it is a promising
material for gas detection.
The material and the concept were applied to a surface
acoustic wave (SAW) sensor as shown in Fig. 70.170
These are high-frequency resonators that can be obtained by
exploiting different acoustic phenomena such as the propagation
of surface acoustic waves (SAW). In SAW devices, the acoustic
wave is excited and detected by a couple of interdigitated
electrodes. The mass sensitivity mechanism is different as com-
pared to QMB. In the case of SAW, the acoustic wave travels at the
surface of the crystal and then it propagates through the sensitive
material. Changes in the mass of the sensitive material elicit
changes in the velocity of the propagation of the acoustic wave.
When the device is connected to a suitable electronic circuit, the
change in the acoustic wave velocity results in changes in the
frequency and phase of the electric signal.171 The frequency of
the wave is determined by the gap between the electrodes and by
the characteristics of materials. SAW can activate signals up to
GHz and the sensitivity of the frequency shift as compared to
mass is still proportional to the square of the fundamental
frequency. Thus, the mass resolution is of the order of fM.
T(2,6-Cl2)PCorrCo has been chosen among the compounds
scrutinized in the abovementioned papers.172 This compound

Fig. 70 (A) Schematic structure of the SAW sensor; the sensitive portion of the device is the space between a couple of interdigitated electrodes. The
gap between the electrodes (40 mm) determines the wavelength of the acoustic wave. (B) Top view of the SAW. Two devices are pictured, one is used as
the sensor and the other as the reference. The Co–corrole film is visible in the magnified view on top of the metal electrodes in particular. (C) A
comparison of the responses measured as changes in the wave phase velocity to form vapors and gases. The concentration is shown in the horizontal
axis label. For H2O, the response to a change from 17% to 22% of relative humidity is plotted. (D) Changes in the response curve to CO in the presence of
various interferents. The green line corresponds to the pure response to CO. In the case of interferents, the sensitivity (the slope of the response curve)
increases or decreases. Adapted from ref. 170, with permission from Elsevier, Copyright 2021.

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shows the selective adsorption of CO and it is also quite easily
obtainable from commercial products.173 Results show that the
affinity between cobalt corroles and CO can be efficiently
transferred to sensors. However, interference studies were
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limited to gases such as O2 and N2, while studies with
porphyrinoids-coated QMBs show that, in general, these mole-
cules are sensitive to a range of volatile compounds.12
The sensing mechanisms of corrole films were studied in
the presence of supramolecular interactions driven by the OH
functionalization of the macrocycle. It was shown that the
decoration of porphyrins with OH groups in the peripheral
position promotes hydrogen bonds between macrocycles, lead-
ing to a regular porous network.174 This approach has been
used with corroles.175 Free-base and Cu, FeCl, and Co com-
plexes of 5,10,15-tris-(3,5-dihydroxyphenyl)corrole were dis-
persed in solvent and deposited onto QMBs. Sensors were
tested with gases and volatile compounds. The sensors were
sensitive to CO and NO with detection limits of the order of
ppm, however the sensitivity to other volatile compounds is not
negligible; in particular, the abundance of OH groups promotes
hydrogen bonds and thus the sensitivity to alcohols. In this
regard, it is important to note that some volatile compounds
(ethanol for instance) can occur at concentrations much larger
than those of CO and NO.
As mentioned above, the inclusion of corroles in porous
organic polymers resulted in better trapping of gas mole-
cules;169 a similar approach was followed with a b-acrolein-
substituted corrole (see Fig. 71).176 The b-functionalization of
TTCorrCo derivatives enabled the introduction of an acrolein
substituent that was co-polymerized with acrolein. The polymers
Fig. 71 (A) Acrolein-substituted Co–corrole complex. (B) SEM image of
corrole-polyacrolein microspheres aggregated onto the quartz microbalance
surface. (C) The dynamic response of hexane shows the increase of the
frequency shift and the shorter response time of corrole-polyacrolein as
compared to the sensors functionalized by the pure elements. (D) A comparison
of sensitivity shows the improved response of corrole-polyacrolein in particular
as compared to alcohols for which the contribution of corroles is larger.
Reproduced from ref. 176, with permission from Wiley, Copyright 2017.
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form microspheres that can adequately form a film on the
surface of a quartz microbalance. The sensor shows the typical
non-selective behavior, also due to the presence of the non-
specific polyacrolein. The presence of corroles induces an
increase in the sensitivity to alcohols and aromatic compounds.
Furthermore, the porosity of the polymers improves the response
time as compared to a pure corrole film.
4.5 Sensor arrays and electronic noses
The examples shown in Fig. 66 and 70 illustrate the differences
between selective and non-selective sensors.
The lack of selectivity exhibited by gas sensors led to the
exploitation of the combinatorial selectivity principle. In this
regard, corrole-based sensors have been included in arrays in
combination with porphyrin-based sensors. The effective
implementation of the combinatorial selectivity principle
requires that the sensors of the array are sufficiently different
from each other. Thus, the modification of the macrocycle
skeleton is an additional, and somewhat powerful, method
for differentiating the selectivity of the sensors.
Sensors based on mass transducers allowed the investigation
of the different contributions from porphyrins and corroles to
the array. QMB sensors were prepared with free-base TPPH2s
and TPCorrH3s and their iron and manganese complexes.177
The responses of sensors to ethanol, triethylamine ethyl acetate
and dimethylformamide were measured. Results showed the
influence of the macrocycle on the sensor sensitivity. The most
striking difference is that the sensitivity of free-base TPCorrH3 is
always larger as compared to the TPPH2. The ratio of sensitivity
between free-base TPCorrH3 and free-base TPPH2 was found to
be correlated to the polar surface area (PSA) of the analytes (see
Fig. 72). PSA is a measure of the total surface contribution of
polar atoms. It is obtained from quantum chemistry calculations
and is used as an indicator in quantitative structure–activity
relationship models.178 The correlation of the increase of sensi-
tivity in corroles as compared to porphyrins suggests that the
additional hydrogen atom in the corrole ring and the consequent
reduction of the molecular symmetry increases the probability of
polar interactions.
Less evident is the role of the macrocycle in the metal
complex. However, TPPFe and TPPMn were found to be more
Fig. 72 (A) TPPH2 and TPCorrH3 were used to functionalize the quartz
microbalance. (B) The ratio of the sensitivities of TPCorrH3 and TPPH2
correlates with the polar surface area of the analyte. Et3N: triethylamine;
DMF: dimethylformamide; EtOH: ethanol; EtOAc: ethyl acetate. Reproduced
with permission from ref. 177, which is an open access article distributed
under the Creative Commons Attribution License (CC BY), MDPI.
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sensitive to triethylamine and dimethylformamide as com-

pared to the TPCorrFe and TPCorrMn.
The additional properties of corroles as compared to por-
phyrins enable the design of sensor arrays that have been
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applied in a number of different areas. In particular, it is worth

mentioning that porphyrin–corroles mixed sensor arrays are
particularly efficient to identify the alterations of volatile com-
pounds in biological samples due to pathologies. The impor-
tance of these studies is based on the evidence that chemical
signals captured in body secretions and excretions contain
information about the cellular processes and ultimately, the
health status.179 Studies indicated that patterns of volatile
organic compounds (VOCs) have been shown to be related to Fig. 73 Score plots of pure compounds as detected by an array of
porphyrins and corroles-coated ZnO nanoparticles. Arrows show the
a vast range of phenomena observable in vitro, even at the
progression of the process of spoilage in whole and ground beef. Repro-
single-cell level,180 and in vivo.181,182 duced from ref. 158, with permission from American Chemical Society,
An OMCorrMn-coated quartz microbalance sensor was used Copyright 2021.
in combination with various metal complexes of TPPH2s in the
first paper, which demonstrated that an array of gas sensors can
discriminate lung cancer via the analysis of exhaled breath.183
OMCorrMn demonstrated a better separation between the
groups of lung cancer and controls as compared to TPPMn.
Similar sensor arrays were used in recent years to measure the
volatile compounds released by murine models to study gene
knockdown in colon cancer,184 the differentiation of pluripotent
human stem cells,185 and the progression of malaria infection.186
A further example of the electronic nose was given by an
array of four resistive porphyrins and corroles-functionalized
ZnO nanoparticles assembled and tested as compared to various
volatile compounds and real samples too.158 The results show
that the array, although limited in terms of the number of
sensors, was sensitive and selective enough to identify the various
compounds. The arrangement of the volatile compounds in the
PCA score plots is similar to the projection of olfactory neurons
into the olfactory bulb where similar compounds were mapped in
closed regions.192 Considering the similarity to the olfactory bulb,
the score plot or any other equivalent representation space can be
considered as a sort of olfactory atlas where the content of
unknown samples can be derived. For instance, in Fig. 73 the
process of the spoilage of meat points towards the region of
amines that are likely the main components in a spoiled meat
sample.

5. Bio-applications of corroles
5.1 Medical imaging applications
Imaging techniques are perfect tools for the diagnosis of many
diseases, including cancers. At the clinical stage, the most
routinely used medical imaging analyses are MRI,187,188 SPECT
and PET,189 with the two latter ones involving the use of radio-
nuclides (Fig. 74).189,190 To increase the contrast in MRI, DOTA
derivatives complexing gadolinium (Gd) are usually used.
In nuclear medicine, e.g. for PET applications, many metals
are currently employed, such as 64Cu (transition metal) and
68
Ga (soft metal), often coordinated by polyazamacrocycles
(DOTA, DOTAGA, NODAGA, TETA,. . .). Corrole macrocycles
Fig. 74 Principal elements used in medical imaging (MRI, PET, SPECT and
Optical Imaging).187–190
can be seen as potentially good candidates for such radio-
nuclide chelation (Cu, Ga,. . .) since corroles display excellent
coordination properties for copper, but also for gallium, whose
68
Ga isotope is increasingly used nowadays in PET imaging.
Interestingly, during the last decade, the concept of coupling
different medical imaging modalities to exploit the comple-
mentarities between two techniques has emerged. Based on
DOTA-like and corrole macrocycles, a folate targeting (Cu)cor-
role–(Gd)DOTA complex that addresses requirements for bimo-
dal MRI and PET imaging was reported (Fig. 75).191

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Fig. 75 The folate-targeting (Cu)corrole–(Gd)DOTA complex (A). An
example of T1-weighted MRI phantoms (4.7 T spin echo method at
25 1C). Tubes 1–4, at different Gd concentrations (1 mM, 50 mM,
100 mM, tubes 1–8) and water (tube 9). (B) Corresponding T1-maps.
Tubes 1–4, at a Gd concentration of 1 mM (tubes 1 and 5), 100 mM (tubes
2 and 6), 50 mM (tubes 3 and 7), 1 mM (tubes 4 and 8) and water (tube 9).
Colored scale in milliseconds. Adapted from ref. 191, with permission from
Elsevier, Copyright 2015.
The corresponding gadolinium Gd(III) complexes were
synthesized and heterobimetallic complexes incorporating
both gadolinium and copper ions were prepared. The over-
expression of the folate receptor in a variety of malignant
tumors, along with its limited expression in healthy tissues,
makes it an attractive tumor-specific molecular target since
‘‘targeting imaging probes’’ is one of the hottest topics in
medical imaging nowadays. The relaxivity values, evaluating
the ability of magnetic compounds to increase the relaxation
rates, were measured. The relaxivity value of the folate con-
jugate with GdDOTA but without the additional corrole ring
was found to be lower (r1 = 2.6 mM1 s1) than the analogs
bearing either a free-base corrole (r1 = 6.4 mM1 s1) or a
copper corrole macrocycle (r1 = 6.3 mM1 s1). However, they
were higher than the actual commercially available contrast
agent ([Gd DOTA H2O], r1 = 4.2 mM1 s1). This may be
explained by the increase in the molecular weight of the
complex (higher than the Gd DOTA derivatives) inducing a
slower molecular tumbling. The values obtained suggest that
such complexes may be promising medical imaging agents for
contrast enhancement in multimodal MRI techniques.188
A triazole-linked corrole/DOTA dyad was prepared by Cu(I)-
catalysed Huisgen cycloaddition between an azido corrole and a
propargyl-DOTA (Fig. 76).192
It was shown that microwave irradiation significantly acceler-
ates the time of the cyclization reaction. The synthesis of hetero-
bimetallic complexes was achieved in up to 60% isolated yield.
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Fig. 76 ‘‘Click’’-linked corrole/DOTA dyad.192
Heterobimetallic complexes were prepared as potential MRI/PET
(SPECT) bimodal contrast agents incorporating, at the same time,
one metal (Mn, Gd) for the enhancement of contrast for MRI
applications and one ‘‘cold’’ metal (Cu, Ga, In) for radionuclide
imaging applications.192 Preliminary relaxivity measurements have
shown that the reported complexes may be promising Contrast
Agents (CA) in MRI.
Metalated corroles have been used as contrast-enhancing
agents for magnetic resonance imaging (MRI).193 Their potential
for tumor-selective delivery was evaluated when encapsulated by a
tumor-targeted polypeptide (Fig. 77). Among the different metals,
manganese corroles exhibit shortening of the T1 relaxation time,
thus leading to enhanced MRI contrast. Manganese complexes can
be seen as attractive alternative MRI active contrast agents since
manganese is, in vivo, one of the essential micronutrients (anti-
cipated to be safe and biocompatible). Interestingly, the MRI
contrast increases considerably after cell entry. Additionally, the
corrole elicited tumor-toxicity through the loss of mitochondrial
membrane potential and cytoskeletal breakdown.
Lanthanide corrole complexes were reported, including
lanthanum (La), terbium (Tb) and gadolinium (Gd) complexes
(Fig. 78), showing for the first time that corrole macrocycle can
be added to the list of potential lanthanide ligands. No MRI
studies were reported in the case of the Gd complex, probably
due to the lack of any water molecule in the coordination sphere
of the central Gd atom, displaying, in this case, a seven-fold
coordination sphere. This Gd complex was nicely prepared by
the metathesis of a Li3 corrole using 1.1 equivalents of GdCl3
salt in the presence of 1.0 equivalent of 1,4,7-trimethyl-1,4,7-
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Fig. 77 The effects of Ga-, Fe-, and Mn–corroles on the T1 relaxation rate
and contrast change. (A) The chemical structure of a metallated sulfonated
corrole. (B and C) T1 relaxation times and contrast images of different
corrole complex solutions in vitro. (D) The measurement of T1 changes
and (E) MR image acquisition after the delivery of indicated doses of CAs.
Reproduced from ref. 193, with permission from Elsevier, Copyright 2015.
Fig. 78 Lanthanide (La, Tb, and Gd) corrole complexes.194
triazacyclononane (TACNMe3).194 The absence of any coordi-
nated water molecule may limit their use as CA in MRI and may
explain why they were not further evaluated as potential MRI
Contrast Agents.
Lanthanide–corrole conjugates were reported based on the
reaction of H4EDTA (ethylenediaminetetraacetic acid) dianhydride
or H5DTPA (diethylenetriaminepentaacetic acid) dianhydride with
a free-base 5,15-bis-pentafluorophenyl-10-(4-aminophenyl)-corrole
(Fig. 79).195 Neodymium (Nd), erbium (Er), ytterbium (Yb) and
lutetium (Lu) lanthanide complexes were prepared, with the
chelation occurring only via the EDTA or DTPA ligands. Photo-
physical studies were carried out and some corrole-sensitized 4f-
luminescence was observed, also showing the time non-quenched
molecular fluorescence of the corrole macrocycle (the presence of
dual emission in the visible and near IR in ambient conditions was
observed).
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Fig. 79 Free-base corrole/DTPA dyads and Ln complexes.195
5.2 DNA binding and G-quadruplex interactions
DNA can lead locally to unusual secondary structures, such as
DNA triplexes or quadruplexes, which result from the assembly
of three or four strands. These non-usual structures represent
natural barriers to DNA replication. They are thus considered as
new targets with high therapeutic value. By stabilizing them
with small molecules,196–198 these structures can stop replica-
tion by preventing the normal progression of enzymes. As a
result, chromosomal instability that is lethal for the cell occurs.
Among these unusual DNA structures, G-quadruplexes are
among the most studied targets. A guanine quadruplex (called
G-quadruplex) is a structure built from the stacking of several
tetrads. The quadruplex structure can be formed by one, two or
four strands of guanine-rich DNA or RNA, in the presence of
monovalent cations such as K+ or Na+. DNA quadruplexes can
be found in telomeric regions or oncogenic promoter regions,
but are not restricted to these.196,199,200
The first report of water-soluble corroles and the study of
their interactions with G-quadruplex was published in 2007 by
Zhou and Yang.201 Two A3-corroles bearing 4-methylpyridinium
or para-trimethylaminophenyl ammonium groups were pre-
pared and studied as G-quadruplex ligands (Fig. 80). These
water-soluble corroles were studied and compared to the clas-
sical, well-studied TMPyP4 porphyrin reference that is well
known as a G-quadruplex stabilizer. They display higher selec-
tivity for quadruplex DNA versus duplex DNA.
In the case of the para-methylpyridinium corrole, five dif-
ferent A3 and trans-A2B-isomers were also prepared202 and
studied by shifting the methylpyridinium unit from the para-
to the ortho- and meta-positions. A significant improvement in
the selectivity for trans-A2B-corroles (para–meta–para, para–
ortho–para methylpyridinium) over A3-corroles (meta–meta–
meta, ortho–ortho–ortho,. . .) was observed.202 Among the metal
complexes (Cu, Mn), manganese corroles bearing pyridinium
groups at the 5,10,15-meso positions were shown to exert higher
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Fig. 80 Water-soluble corroles able to interact with the G-quadruplex.201
stabilization effects of the G-quadruplex structure.203 A gallium
complex of 5,10,15-(N-methyl-4-pyridyl)corrole was also synthe-
sized and its binding properties with c-MYC G-quadruplex
DNA, a potent target for antitumor drugs, was investigated.
It was shown that this gallium corrole can strongly bind to
c-MYC G-quadruplex DNA mainly via a groove binding mode.
Interestingly, under light irradiation, greater toxicity towards
Hep G2 cancer cells was observed.204
5.3 Antiviral activities
Whereas bacterial infections can usually be treated with differ-
ent classes of antibiotics, this is not the case for viral infections
for which treatments are currently limited. Viruses are intra-
cellular parasites that use the cellular functions of their hosts to
enter the cell and replicate. They are known to adapt to
treatment and develop resistance, leading to treatment failure.
In order to avoid damaging the host cell, antiviral treatment
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must be able to influence viral biology without altering cellular
functions. Although several treatments have been developed for
a specific viral infection, broad-spectrum antivirals have yet to
be developed. Therefore, there is a constant need for new
generations of first-in-class anti-viral molecules that could be
positioned in first-line treatment or in combination with pre-
existing therapies. New antivirals should demonstrate increased
efficiency, reduced side effects and high potency toward resistant
strains.
Human cytomegalovirus (hCMV) is a member of the herpes
virus family. It usually infects up to 80% of the general
population with a prevalence rate reaching more than 90% in
high-risk persons (e.g. unborn babies whose mothers become
infected with CMV during the pregnancy or people with HIV).
CMV is a common virus that infects people at any age and once
you have been infected, the virus remains all your life. Most
CMV primo-infections are silent, and most of the people who
are infected have no signs or symptoms. However, CMV is the
first cause of blindness in HIV patients and the first cause of
foetal malformations in the case of primo-infection during
pregnancy. Unfortunately, many previous vaccine approaches
failed to provide complete protection against CMV. Antiviral
drugs can slow virus multiplication but they cannot cure it as
they do not act on the virus reservoir. Nowadays, most of the
existing drugs used to treat CMV are nucleoside derivatives
such as ganciclovir, valaciclovir, and cidofovir that inhibit viral
replication by acting as fraudulent building blocks for viral
DNA synthesis. These drugs may sometimes display adverse
effects, such as myelosuppression and nephrotoxicity. They can
lead also to the emergence of antiviral resistant CMV strains
during long-term or repeated treatments.205–208 Recently, in the
antiviral research field, numerous studies have been devoted to
the development of non-nucleoside CMV inhibitors with novel
mechanisms of action. New antiviral drugs must lead to more
selective compounds with a broad spectrum of antiviral activity
and, if possible, little or no drug-resistance induction.
Over 200 porphyrins and porphyrin derivatives were
screened against hCMV and a lead corrole molecule was identified
that displayed very interesting antiviral properties (Fig. 81).209
Compared to the porphyrin analog, TNPCorrH3 showed the stron-
gest inhibitory effect on both the infection rate and activation of IE
(Immediate Early) expression. Hit corrole isomers have also been
shown to possess strong inhibitory effects on hCMV infection with
reduced in vivo toxicity. Interestingly, porphyrin analogs (e.g.
bearing nitro substituents on the meso-phenyl rings) of the hit
corrole were tested for comparison but they did not display any
potent antiviral activities.
A small library of nitro- and fluoro-corrole derivatives,
directly inspired by the first corrole hit, was then developed
during a Structure–Activity Relationship (SAR) study (Fig. 82
and 83).210,211
Metalated corroles (e.g. Mn, Cu) did not present any good
antiviral activity and only free-base corroles bearing one or
several EWG groups (e.g. –NO2 group) on the para-position of the
5,10,15-meso-phenyl ring displayed valuable antiviral activities.
Based on a step-by-step SAR study (Fig. 86), forty-three different
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Fig. 81 Identification of the first hit.209

corroles were prepared and fully characterized. Different A3-

corroles bearing one lipophilic halogen atom (e.g. –F, –CF3, or
–Cl) and one nitro group on the phenyl rings were synthesized
(Fig. 87). Some of the corroles differed only in the position of the
fluorine, e.g. from the ortho- to meta-position or by the number of
fluorine atoms.
A3- to trans-A2B-corroles were prepared to further study the
effect (if any) of the symmetry of the corrole. The most interesting
antiviral properties were obtained in the case of fluorinated-
corroles without any strong –EWG group. The synthesis of differ-
ent A3-corroles bearing fluoroaryl substituents at the meso-
positions was thus carried out by varying the number from one
to five, and also the position (ortho, meta, para) of the fluorine
atoms. The permutation of the meso-aryl groups at the 5,15- to the
10-position was also studied.
Working with the human pathogenic poxvirus requires high-
confinement laboratories for class 3 (Monkeypox virus, MPXV)
and class 4 (Variola virus, VARV) viruses and very high security Fig. 82 Structure–activity relationship study.210,211
levels. One way to further investigate the antipox virus activity
of compounds is to work with lower-confinement poxviruses
good PK/PD profile.212 Including recent studies on hCMV, the
such as the myxoma virus (MYXV). This leporipoxvirus is known
authors have demonstrated that corrole macrocycles can now be
to induce severe disease in rabbits and can serve as a good
seen as very promising agents displaying broad-spectrum anti-
model to study the broad antiviral properties of any new corrole
viral activities against dsDNA viruses. By comparison, the por-
macrocycles. Very recent results have demonstrated that free-
phyrin analogs are less efficient than their corrole counterparts.
base corroles can be very effective on viruses of the poxvirus
family, opening up perspectives in animal health and defense.
Indeed, after screening more than 40 different corroles, a hit 5.4 Antibacterial activities and photodynamic inactivation
was identified, namely Fluocovir (corrole 35, Fig. 83). Fluocovir (PDI)
was injected at up to 100 times that of in vitro IC50 on New Numerous porphyrin derivatives have been tested as potential
Zealand white rabbits without any sign of acute toxicity (Fig. 84). antimicrobial agents in photodynamic inactivation (PDI).
Rabbits were infected at day one by the injection of 80 plaque- Recent reviews highlighted the main advances in the field
forming units (pfu) of the Myxoma virus wild-type strain in the and illustrated the structures of the porphyrin compounds
dermis of the left ear. Interestingly, in vivo studies showed tested and their efficiencies.213–215 Some cationic gallium corroles
symptom delay and animal weight increase upon treatment. bearing ortho or para-methylpyridinium moieties have been pre-
Fluocovir was shown to display nanomolar antiviral activities pared (Fig. 85)216 and their antibacterial activities against the
even on resistant strains and is active on a large variety of Gram-negative bacterium A. fischeri were evaluated and com-
dsDNA viruses. Moreover, the optimized compounds exhibit a pared to TMPyP4, a well-known reference in biological studies.

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Fig. 83 Selected structures among the 43 corroles tested against the
pox-virus.212
Corrole with the para-methylpyridinium was shown to display,
at lower doses, notable efficiency when compared with TMPyP4.
Total photoinactivation was achieved after 45 min of irradiation.
It was concluded that positively charged metallocorroles were
potentially more efficient than the neutral analogs to photo-
inactivate the Gram-negative bacterium A. fischeri and without
any dark toxicity. Anionic and cationic tin and phosphorus
corroles were prepared and used as photosensitizers, in combi-
nation with low doses of white light, to inhibit the germination
of mold fungi spores.217 Three different model organisms e.g.
Aspergillus niger, Cladosporium cladosporoides, and Penicillium
purpurgenum were studied since nowadays, mold fungi are
responsible for many allergies or other health problems. Inter-
estingly, the positively charged corrole complexes have been
shown to induce complete damage of the conidia. They were
able to attenuate germination upon light exposure without
displaying dark toxicity.217 These preliminary results pave the
way for further use of cationic corroles in antimicrobial photo-
inactivation applications.
Corrole-grafted-chitosan films were prepared (Fig. 86)218 by
the direct reaction of TPFCorrH3 with chitosan, followed by
solvent casting. Chitosan is an amino-polysaccharide usually
extracted from the skeleton of shellfish and usually produced by
the deacetylation of chitin. Therapeutic applications have been
proposed because chitosan displays several interesting properties
such as antioxidant activity, cholesterol and triglyceride trapping.
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Fig. 84 Fluocovir tested on the clinical hCMV Letermovir-resistant strain
(top) and on the pathogenic poxvirux MYXV (bottom), both viruses being
ANCHORTM tagged.212
Chitosan usually shows good antibacterial properties, good
adsorption to mucous membranes and low toxicity.219 It can
be seen as a promising material for drug encapsulation as it can
lead to covalent or non-covalent interactions. It also possesses
some hypoglycemic effects and can be further used for the
prevention and treatment of chronic diseases. The transparent
films obtained by the authors have been shown to display
interesting fluorescence properties as well as bacteriostatic
properties against S. aureus, suggesting possible future applica-
tions of such corrole-modified films as biosensors, bioimaging
agents, or bioactive optical devices.218
5.5 Photodynamic therapy (PDT) applications
PDT (Photodynamic Therapy) is a treatment used via a photo-
sensitizer and a light source to selectively kill cancer cells
through the localized production of singlet oxygen.220,221 How-
ever, the depth of light penetration into the tissue remains an
obstacle to this therapy.222
It was in the 1970s that derivatives of the hematoporphyrin
HpD (Hematoporphyrin Derivative) were more widely studied.223
An active fraction of HpD was isolated and marketed in 1985
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Fig. 85 Cationic gallium corroles bearing ortho- or para-methylpyr-
idinium moieties.216
under the name Photofrins. Other photosensitizers based on
porphyrins or corroles have been developed to get closer to the
ideal pigment, which must meet precise specifications: the
photosensitizer must ideally have a high molar extinction coeffi-
cient in the near infrared or red, and a high quantum yield in
singlet oxygen. It must also be selective to the tissue to be treated,
slightly or non-toxic in the absence of light, and rapidly elimi-
nated from the body after treatment. One key parameter to
consider is the cellular uptake and subcellular localization of
the photosensitizer (involving morphological cells changes but
also cytotoxicity after PDT treatment). Several reviews have been
reported with a quite exhaustive state-of-the-art utilization of free-
base or metalated corroles as photosensitizers in cancer photo-
dynamic therapy.13,213,223–234
Different A3- and trans-A2B-corroles were synthesized and their
gallium complexes were prepared and studied as potential photo-
sensitizers in PDT (Fig. 87).235–241 Corrole conjugates have been
the subject of a recent review from Sessler and coworker.242 Main
group corroles and their photophysical properties have been
recently reviewed by Gross and Churchill.243 The correlation
between the molecular structures of three free-base A3-corroles
(e.g. TPCorrH3, TPFCorrH3 and TpMCPCorrH3) and their effi-
ciencies for singlet oxygen generation was recently reported.244
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Fig. 86 Corrole-grafted-chitosan films.218
Near-Infrared emitter tris-ethynyl gallium(III) corroles were
recently reported (Fig. 88).245 Compared to the Ga(III) pyridine
complex of 5,10,15-tris-pentafluorophenylcorrole, the ethynyl
corroles displayed shifted bathochromic absorption to the
near-infrared region, the trend being larger upon increasing
the p-conjugation. The (pyridino)-5,10,15-tris-pyrenylethynyl-
corrolato gallium(III) displayed an intense and broad Soret Band
at 510 nm, an emission maximum at 740 nm and a fluores-
cence quantum yield of 0.27 in aerated toluene, whereas the
A3- and trans-A2B-electron-poor-NO2 corroles exhibited
quenched emission, due presumably to the EWG –NO2 groups.
Several phosphorus corrole complexes were reported in the
literature (Fig. 89).246–250 A theoretical study was reported by De
Simone, Russo and coworkers.246 They confirmed by DFT and
TDDFT computational studies that phosphorus iodinated-
corrole complexes possess all the requirements to be further
used as photosensitizers.
Among the required properties, (i) they strongly absorb in a
region close to the NIR region, (ii) their singlet–triplet energy gap was
shown to be large enough to excite the molecular oxygen and to
generate cytotoxic ROS.246 A TECorrP was reported, which was
shown to be a potentially efficient and non-toxic photosensitizer for
PDT.250 Interestingly, the chemical and physical properties of phos-
phorus corroles can be fine-tuned for diverse applications.248,251
Rhenium,252,253 iridium254,255 and osmium256 corrole complexes
have been reported (Fig. 90). Rhenium(V)–oxo triaryl corroles
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Fig. 87 Gallium A3- and trans-A2B-corrole complexes tested as potential
photosensitizers in PDT.235–241
Fig. 88 Ethynyl gallium corroles.245
bearing at the meso-positions some methyl ester or carboxylic
acid functional groups at either the meta- or para-position of the
three phenyl rings, have been described.252,253 Differences in
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Fig. 89 Phosphorus and phosphorus-iodinated-corrole complexes.246–250
the phosphorescence quantum yields and phosphorescence
lifetimes were observed between the ester (around 1%) and the
corresponding carboxylic acid analogs (around 0.01%). Interest-
ingly, the quantum yields for singlet oxygen formation were
found to be quite high for both the ester and the corresponding
carboxylic acids, showing high potential for further applications
in PDT. Iridium(III) corroles were reported,254,255 showing inter-
esting phosphorescence properties and the ability to produce
singlet oxygen with 10–15% efficiency (the phosphorescence
quantum yield turned out to be low, about 0.02–0.04% at
ambient temperature but two complexes were found to efficiently
sensitize singlet oxygen formation with quantum yields F(1O2)
equal to 0.71 and 0.38 for L = pyridine and 4-picolinic acid,
respectively).254 Nitrido-osmium(VI) corroles256 were shown to
display room temperature NIR phosphorescence with lmax in
the range 779–795 nm. They are potentially good sensitizers of
singlet oxygen with 1O2 quantum yields in the range 0.76–0.95.
Interestingly, they represent a new class of NIR phosphorescent
dyes with high photostability and relatively long decay times.
Some tin complexes were reported (Fig. 91).257–259 By com-
parison with the free-base analogs, it was shown that the Sn(IV)
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Fig. 90 Rhenium,252,253 iridium254,255 and osmium256 corroles.
tris-2-thienyl- and triarylcorroles possess higher FD quantum
yields, likely due to the heavy atom effect associated with the
tin metal ion, making them good candidates for PDT applica-
tions. Interestingly, if we compare them with the triphenylcor-
role analog, the tris-2-thienylcorrole shows quite an important
red-shift of the last Q band, enhancing its absorption close to
the therapeutic window.
(SO3)2TPFCorrFe derivatives have been prepared (Fig. 92).260–263
They were studied as potential cytoprotective agents (e.g. evaluated
for their neuroprotective/neurorescue activities) against oxida-
tive nitrative stress, more particularly in cellular models
of neurodegeneration induced by the Parkinson-related
neurotoxin 6-hydroxydopamine or the peroxynitrite donor
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Fig. 91 Tin corrole complexes.257–259 Adapted from ref. 257, with per-
mission from the Royal Society of Chemistry, Copyright 2019.
Fig. 92 Molecular structure of (SO3)2TPFCorrFe.260–263
3-morpholinosydnonimine. The iron(III) corroles were found
to be more efficient than the manganese(III) analogs in further
promoting neuronal survival (in the experimental conditions
used by the authors). Thus, they can be considered for further
applications in the treatment of degenerative disorders of the
peripheral or central nervous systems (CNS).
After the report of the first gold complexes based on the
corrole macrocycle,92,265,266 a water-soluble gold(III) corrole was
reported and its cytotoxicity, as well as its cytostaticity, were
evaluated (Fig. 93).264 Amphiphilic gold tris(carboxyphenyl)-
corroles were also reported by Gederaas, Vinogradov, Wanser,
and Ghosh.92 More recently, gold complexes of a series of
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Fig. 93 Gold corrole complexes.264
tetra-b-substituted TPFCorrH3 (Y = –Br, –I or –CF3) were
reported,267 as well as their phosphorescence properties stu-
died in different solvents. Interestingly, the tetra-iodinated gold
corrole exhibited an important red shift absorption, whereas the
tetra –CF3 Au corrole showed the most redshifted room tempera-
ture phosphorescence spectrum. Solvent dependence of the
phosphorescence lifetimes (as well as the intensity) was also
observed.267
Two platinum-bipyridyl corrole isomers were prepared and
fully characterized (Fig. 94).268 The para isomer, as a free-base,
was first prepared via the Heck cross-coupling reaction between
10-(4-bromophenyl)-5,15-bis(pentafluorophenyl)corrole isomers
and 4-vinylpyridine but some difficulties were encountered. A
second pathway was used by the pre-functionalization of the
aldehyde with the vinyl unit, followed by classical condensation
with 5-(pentafluorophenyl)dipyrromethene. The platinum com-
plexes were prepared in good yields (between 75–80%) using cis-
dichloro(2,2 0 -bipyridine)platinum(II) at 50 1C in DMF. Binding
studies with DNA and HSA were carried out by fluorescence
studies and gel electrophoresis. Interesting interactions were
observed268 with calf thymus DNA, HSA, and plasmid DNA,
Fig. 94 Platinum-bipyridyl corrole isomers.268
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Fig. 95 TPFCorrH3 conjugates bearing one or two b-cyclodextrins.269
further showing that such platinum-bipyridyl corroles can
be considered as interesting candidates for further DNA-
interaction applications.
To increase their water solubility, some TPFCorrH3 conju-
gates bearing either one or two b-cyclodextrins were prepared
and their photocytoxicities towards HeLa cells were evaluated
(Fig. 95).269 It was shown that such conjugates, as well as the
non-conjugate corrole, were able to generate singlet oxygen and
to be cytotoxic, depending upon light exposure level and dose
concentration.270 Fluorescence microscopy revealed HeLa cells
localization in dictyosomes and mitochondria.
The DNA-binding, photocleavage, and photodynamic anti-
cancer activities of free-base and metalated corroles were
reported.271 A3- and trans-A2B-pyridyl corroles bearing either
one or two pentafluorophenyl substituents at the meso position
were prepared and it was shown that these pyridyl-corroles
display binding affinity to CT-DNA and can photocleave pBR322
DNA.271 The binding affinity toward CT-DNA was shown to
decrease when the number of pentafluorophenyl aryl groups
increased, whereas the photocleavage activity toward pBR322
DNA became more efficient.
A cationic iron corrole was isolated as a di-iron(IV) m-oxo
dimer, whereas the manganese complex of the same corrole
was isolated as a manganese(III) monomer.205 Two different
binding modes were observed, depending on the nature of the
metal: the Mn(III) corrole complex interacts with CT-DNA
through an outside groove binding mode, while the di-iron(IV)
m-oxo dimer may bind differently via an outside binding mode
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Fig. 97 Free-base and cobalt corroles with –OH or phenothiazine

group.276

spectroscopy. It was shown that an ultrafast electron transfer

ET between (SO3Na)2TPFCorrGa and the guanine bases of ct-
DNA occurred within the pulse duration equal to 156 fs.273
Cobalt(III) mono-hydroxyl and phenothiazine corrole com-
plexes were prepared and studied (Fig. 97).276 It was shown that
both cobalt complexes displayed quite low levels of dark toxicity
and interestingly, they showed high photocytotoxic activity
against HeLa, H460, and A549 cell lines. Both cobalt complexes
may thus have potential application in PDT as a photosensitizer.
Different manganese corrole complexes were synthesized
and fully characterized (Fig. 98).205,206 The DNA-binding prop-
erties of cationic manganese(III) corroles were evaluated. It was
shown that the Mn(III) complexes interact with circulating
Fig. 96 Structures of the halogenated gallium corroles272 and the anionic tumor deoxyribonucleic acid (CT-DNA) through an outside
disulfonic corrole gallium corrole.273 groove-binding mode and by comparison, the diiron(IV) m-oxo
corrole complex (based on the same free-base corrole structure)
was shown to interact in a difunctional binding mode. A similar
in low concentrations. At higher concentrations, the di-iron(IV)
m-oxo dimer was shown to stack in the major grooves of the
duplex but could also partially intercalate into DNA. In the
presence of H2O2 or even better with tert-butyl-hydroperoxide
TBHP oxidant, both metal complexes were shown to catalyze
the oxidative cleavage of pBR322 plasmid DNA.
Two methyl benzoate gallium(III) corrole complexes, 10-(4-
methoxycarbonylphenyl)-5,15-bis(pentafluorophenyl)corrolato-
gallium(III) and 5,15-bis(4-methoxycarbonylphenyl)-10-(penta-
fluorophenyl)corrolatogallium(III), were synthesized and studied.
Both gallium(III) corrole complexes interact with DNA via major
groove binding. Under irradiation, they were able to cleave DNA
quite efficiently (Fig. 96).272
The same year, a (trans-dihydroxo)phosphorus(V) complex of
10-(4-hydroxylphenyl)-5,15-bis(pentafluorophenyl)corrole was
reported.274 This P(V) complex can bind DNA via an outside
binding mode. Some photocleavage activity was also observed
occurring via hydroxyl radical, singlet oxygen, and superoxide
anion formations. More recently, an oxo(corrolato)chromium(V)
complex was reported207 that selectivity damaged leukemia
cancer cells.
A series of halogenated gallium corroles was reported, which
could bind CT-DNA via an outside binding mode. Under illumina-
tion, they were able to efficiently produce singlet oxygen species,
displaying good antitumor activities against HepG2 cells.275
An anionic disulfonic gallium corrole was previously
reported and studied by femtosecond transient absorption Fig. 98 Push–pull manganese corrole complexes.277

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interaction was observed only at low concentration, while at
higher concentration the iron dimer complex mainly stacks in
the major grooves of CT-DNA.205
Push–pull manganese(III) corroles bearing –NO2 EWG at the
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5,15-meso-positions and different EDG at the 10-meso-position
(e.g. –OCH3, –NMe2) were reported. In solution, it was shown
that manganese complexes of such trans-A2B-corroles interact
Fig. 99 Reported tetra-thiocyanatocorroles obtained after light irradia-
tion (top) and UV–vis absorption spectra of TPFCorrH3 (green line), and
2,3,17,18-tetrathiocyanato-5,10,15-tris(pentafluorophenyl)corrole (blue
line), in acetonitrile (bottom). Adapted from ref. 278, with permission
from American Chemical Society, Copyright 2021.
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strongly with circulating tumor deoxyribonucleic acid
(CT-DNA). Interestingly, the strength of the interaction can be
increased when a stronger EDG group is introduced at the
10-meso-position.277
Very recently, the photocatalytic tetra-thiocyanation of free-
base corroles using ammonium thiocyanate was reported
(Fig. 99).278 The irradiation was carried out at room tempera-
ture in acetonitrile using a standard 20 W CFL (Compact
Fluorescent Lamps) lamp. The tetra-thiocyanatocorrole was
the main isolated compound after 5 hours of reaction. It is
possible to monitor the reaction by ESI or MALDI mass spectro-
metry using the negative mode detection. Two reviews reported
the best matrix and conditions to use when running MALDI/
TOF279 or ESI280 mass spectra for small molecules or corrole
derivatives. Very interestingly, the UV-visible spectra of the
isolated tetra-thiocyanatocorroles show, in acetonitrile, the
presence of four Q-bands, quite similar to the Q-type bands of
chlorophyll-a. Thus, these b-substituted corroles can be considered
as spectroscopic model systems of the latter. A mechanism was
proposed, involving radical species, and the formation of radical
anion species was further confirmed by EPR.278
5.6 Fluorescent heme proteins
Very recently, Lemon and co-workers reported the synthesis of
fluorescent heme proteins by the incorporation of a phos-
phorus corrole into two stable heme proteins: H-NOX from
Caldanaerobacter subterraneus and heme acquisition system
protein A HasA from Pseudomonas aeruginosa (Fig. 100).281
The binding of the corrole in the heme pocket of the protein
was confirmed by emission and absorption spectroscopy,
demonstrating the proof-of-principle and the possibility to
Fig. 100 Phosphorus corrole-substituted fluorescent proteins. Adapted
from ref. 281, with permission from American Chemical Society, Copyright
2021.
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further develop new fluorescent proteins. Interestingly, these

corrole-substituted heme proteins were shown to exhibit
more intense fluorescence (in a narrower spectral profile) than
traditional fluorescent proteins that emit in the same spectral
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window.281 It was shown also that the corrole emission

was enhanced in the HasA conjugate but was quenched in
the H-NOX.

6. Synthetic advances
6.1 Scale-up and optimization of Gryko’s method
To further develop corrole-based applications in different
fields, such as sensors, catalysis, biology or medicine, one
has to consider not only the use of smooth and easy synthetic
methods with few steps to access A3- or trans-A2B-aryl-corroles
(this is in fact the case in corrole chemistry) but also the
possible scale-up from milligrams/centigrams to grams, from
grams to decagrams or hectograms. In 2006, the gram synthesis
of corrole at the 20 mmol scale was reported by Gryko and
Koszarna via a very efficient synthesis involving the use of a
water–methanol mixture.282 In 2010, Nocera and co-workers
reported the gram-scale (1.34 g) synthesis of TPFCorrH3283
following a modified Lindsey porphyrin forming reaction.284
Recently, Bröring and co-workers reported the gram-scale
synthesis (starting from 20 mmol of dipyrromethane) of 5,15-
pentafluorophenyl-10-(4-(carboxy)phenyl)corrole using Gryko
conditions.285 To further develop biological applications and to
consider possible clinical applications, in vivo tests on small
animals (rats, rabbits,. . .) may require quite a lot of corrole Fig. 102 Pictures of the scale-up synthesis of Fluocovir carried out in 4 L
three-neck flasks.212
macrocycles, at least at the decagram scale. Recently, the synthesis
of around 25 g of 5,15-bis(20 ,30 ,50 ,60 -tetrafluorophenyl)-10-
(pentafluoro-phenyl)corrole, administered to 25 rabbits during 75 g of dipyrromethene, prepared starting from 2.5 kg of pyrrole,
in vivo studies, was reported.212 At a first glance (Fig. 101), the 65 g of tetrafluorobenzaldehyde and 35 g of MgBr2. The amounts
synthesis of around 20–25 g of free-base corrole requires at least of solvents and reagents during the bilane synthesis steps was
estimated as 13 liters of methanol, 13 liters of water and 650 mL of
HCl, 37%. To secure the scale-up, the authors carried out eleven
syntheses, one after the other, starting in each case from penta-
fluorobenzaldehyde (1 eq.) and varying the number of moles of
HCl from 244 mM (yield 12.5%) to 608 mM (yield 30.4%).
Around 65 liters of chloroform were required, as well as 80 g
of DDQ. After optimization (Fig. 102), 24.6 g of pure corrole was
isolated via eleven different synthesis batches that were, at the
end, all combined in the same vial.
Interestingly, during the synthesis, the authors found that
the isolated yield was clearly dependent upon the concentration
of HCl, with the greater amount of HCl leading to the higher
yield in 5,15-bis(2 0 ,3 0 ,5 0 ,6 0 -tetrafluorophenyl)-10-(pentafluoro-
phenyl)corrole. This free-base corrole was denoted as Fluocovir
for further in vitro and in vivo studies.212

6.2 Recent discovery of corrole bearing meso directly linked

COOH groups
Very recently, the corrole family was enlarged (Fig. 103) with the
arrival of a newborn: a tris-meso-carboxylate corrole, potentially
Fig. 101 Scale-up synthesis of Fluocovir.212 bringing new important applications in medicinal chemistry.

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evaluating its ability to interact with plasma proteins but also to be

used as a catalyst for the decomposition of hydrogen peroxide. In
the latter case, a very efficient formation of molecular oxygen was
observed when hydrogen peroxide was added to an aqueous
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solution of human serum albumin (HSA) in the presence of the

iron complex of corrole meso-triscarboxylate. Different triscarbox-
ylate corroles are now available for further medicinal and drug
applications (Fig. 103).

6.3 Dipyrrin-bisphenol: corrole analogs

Recently, a ligand analogy was found between different metal
complexes of dipyrrin-bisphenol and the corrole macrocycle
(Fig. 105).289–291 Dipyrrin-bisphenol is a tetradentate ligand,

Fig. 103 A newborn in the corrole family: a tris-meso-carboxylate

corrole.286

Gross et al. reported, for the first time, the straightforward synth-
esis of a tris-meso-carboxylate corrole obtained by the hydrolysis of
the meso-CF3-substituted metallocorroles (Fig. 103).286 Surpris-
ingly, it was not synthesized by the hydrolysis of the ethyl ester
analog (Fig. 104) as previously described287,288 but by the hydro-
lysis of the meso-CF3-substituted corrole metal complexes
(Fig. 103). A mechanism was proposed, occurring via the nucleo-
philic attack of the hydroxide anion and followed by several
intermediates. In medicinal chemistry, the pharmacokinetic prop-
erties of a potential drug candidate, such as absorption, distribu-
tion, metabolism, and excretion, have to be evaluated. Lipinski’s
rule of five of this new tris-meso-carboxylate corrole was discussed,
showing that this new corrole macrocycle is close to having the
chemical and physical properties for potential per os (oral) admin-
istration. The iron complex was tested, as a proof of concept, by

Fig. 105 Ligand analogy between corrole and dipyrrin-bisphenol (top)

free-bases and (bottom) bis-ammonia cobalt complexes. Adapted from
ref. 290, with permission from American Chemical Society, Copyright
Fig. 104 meso-Ester corroles previously described.287,288 2019.

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Table 1 A comparison of selected geometric distances (Å) and angles (1)
of bis-NH3 DPPCo and a previous bis-ammonia cobalt corrole complex
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but not allowing a complete elucidation of the potential of this
macrocycle for practical applications. This situation drastically
changed in the new millennium, thanks to the report of
practical routes for the preparation of triarylcorroles,3,4 which

boosted the number of studies involving corrole derivatives.

Due to the effort of different groups, the synthetic chemistry of
corroles is now well developed,15 reaching the versatility of the
Structures
parent porphyrins and probably being the most developed in
Bond distances (Å) Bis-NH3 DPPCo Bis-NH3 cobalt corrole the large family of porphyrin analogs. The rational functiona-
Co–Npyrrole 1.913(3) 1.909(3) 1.893(6) 1.908(6) lization of the corrole ring is also possible, thanks to the
Co–O/Npyrrole 1.919(2) 1.905(2) 1.868(6) 1.881(6) unexpected but advantageous regioselectivity showed by
Average
Co–Npyrrole/O 1.912(6) 1.888(17) corrole,15 despite the low symmetry of the molecular skeleton.
Co–Nammonia 1.963(3) 1.938(3) 1.964(6) 1.974(6) The coordination chemistry of corrole is also well developed.
Average These achievements can allow the fine-tuning of corroles
Co–Nammonia 1.951(18) 1.969(7)
and their metal complexes for particular applications, and have
Bis-NH3 cobalt allowed the flourishing of corrole applications. In this review,
Bond angles (1) Bis-NH3 DPPCo corrole we have summarized the most recent results obtained in
O/Npyrrole–Co–Npyrrole 83.10(10) 91.82(11) 95.1(3) 91.5(2) different fields, ranging from catalysis to clinical applications.
Npyrrole/O–Co–Npyrrole/O 93.35(12) 83.10(10) 81.5(2) 91.9(3) Initially, the first reports focused on the exploitation of metal-
Average locorroles as oxidation catalysts, due to the assumption that
O/Npyrrole–Co–Npyrrole 88(6) 90(6)
Average corrole stabilizes the higher oxidation states of coordinated
Npyrrole/O–Co–Nammonia 90(1) 90(2) metals as compared to porphyrin. However, the elucidation of
the peculiar properties of this macrocycle has stimulated
interest in the exploitation of corroles in different fields,
like corrole and porphyrin, and interestingly, its chemical making the portfolio of corrole applications much broader.
structure can be seen as the combination of half a salen unit For some of these applications, a series of investigations
and half of a porphyrin macrocycle (Fig. 105). What makes the already evidenced the potential of corrole derivatives. This is
dipyrrin-bisphenol ligand closer to a corrole (and not a por- the case of the applications of corroles as catalysts: while the
phyrin) is that it presents, like corrole, a formal 3 charge and exploitation of metallocorroles as oxidation catalysts was the
this molecule is able to coordinate quite a large variety of non- first studied, more recently, corrole complexes have demon-
metal or metal ions such as boron,292 manganese,291 cobalt,290 strated interesting performances as non-precious metal electro-
gold.289 Dipyrrin-bisphenol is a 12 p-conjugated system with catalysts for water splitting reactions, which are fundamental
only one meso-position and 4 beta-pyrrolic positions. As in the processes for conversion energy devices. In these reactions
case of the corrole macrocycle,8,293–298 some innocent or non- (HER, OER, ORR) Mn, Fe, and Co corroles have demonstrated
innocent character of the ligand can be encountered, depend- important properties that make them potential substitutes for
ing on the nature of the metal or non-metal ion. In the case of the expensive Pt catalysts.
the cobalt complexes, it was shown that the changes in the aryl Further studies are necessary to optimize the performances
substituents on the single meso-position can also change the of the corrole catalysts; a breakthrough in these studies will
spectroscopic, electrochemical and ligand binding properties provide a standard procedure for comparing the results reported
of the complex. The oxidation state of the cobalt dipyrrin can in the literature. Without this rational approach, it is quite
change in bonding and non-bonding solvents. difficult to have a clear picture of all the different parameters
The comparison of the X-ray structures of the cobalt bis- that could be tuned (peripheral substituents, coordinated metals,
ammonia complexes of corrole and dipyrrin-bisphenol is of solid supports, deposition techniques, etc.) to optimize catalyst
interest (Table 1). Despite structural differences between these performances.
two ligands, the bond angles and the principal distances in the For other fields, the application of corroles is far less
two metal complexes are of the same order of magnitude, explored; some promising examples of chemical sensors based
showing that dipyrrin-bisphenol can be considered as an on corrole derivatives as sensing materials have been reported,
excellent analog of corrole, worthy of further investigations or taking advantage of, for example, the optical features of corrole
comparison studies. derivatives. In this area, corroles can provide a great contribu-
tion to the development of cross-sensitive sensor arrays
7. Summary and outlook together with porphyrin sensing materials. This approach can
allow the development of reliable devices in the next few years,
Corrole chemistry has had a long infancy period, starting from whose application can be fruitful in different fields, such as
the first report in the early sixties. Until the new millennium, environmental monitoring and clinical analysis.
only a few studies on this macrocycle were reported in the Another area where corroles can have important applica-
literature, shedding light on the peculiar properties of corroles tions in the next few years is the clinical field. The peculiar

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optical properties of corrole derivatives make them obvious 5,15-dpM-10oMCorrH3 5,15-Bis-(4-methoxycarbonyl-

candidates as photosensitizers in PDT, while Mn- and even phenyl)-10-(2-methoxycarbonyl-
lanthanide-conjugated complexes have been exploited as phenyl) corrole
contrast-enhancing agents for MRI. In this area, a promising DOTA 1,4,7,10-TetraazacycloDOdecane-
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application of corrole derivatives is their exploitation as anti- 1,4,7,10-TetraAcetic acid

viral drugs, where preliminary studies have demonstrated DSSC Dye sensitized solar cell
unique properties of this contracted macrocycle. DTPA Diethylenetriaminepentaacetic
It is worth mentioning that all these applications cannot be acid
possible without further synthetic progress, which should allow EDG Electron-donating groups
the gram-scale syntheses of target corroles. Also, on this scale, EDTA Ethylenediaminetetraacetic acid
important novel protocols have been recently reported and the EPG Edge-plane graphite
definition of novel corroles, such as corrole tris-carboxylates, EPR Electron paramagnetic resonance
and the improved characterization of their properties, will lead ESI Electrospray ionization
to tumultuous progress of the field in the next few years. EWG Electron-withdrawing groups
For this reason, we can affirm that corrole chemistry is now Fluocovir 5,15-Bis(2 0 ,3 0 ,5 0 ,6 0 -tetrafluoro-
reaching maturity and corroles are ready to go to work in many phenyl)-10-(pentafluorophenyl)-
different applied fields. corrole (anti-viral Hit)
FRET charge transfer Förster resonance energy transfer
charge transfer
Author contributions FTO Fluorine-doped tin oxide
(electrode)
The authors contributed equally to this work.
hCMV Human CytoMegaloVirus
H4EDTA Ethylenediaminetetraacetic acid
Abbreviations H5DTPA Diethylenetriaminepentaacetic
acid
ANCHOR ANCH sequence cloned upstream HER Hydrogen evolution reaction
of the OR-FP expressing gene HpD Hematoporphyrin derivative
10-az-DFPCorrH3 5,15-bis-pentafluorophenyl-10- HSA Human serum albumin
(4-azidophenyl)corrole HTM Hole transporting material
BHJSC Bulk-heterojunction organic solar 10-HDPCorrH3 10-(4-Hydroxylphenyl)-5,15-
cells diphenylcorrole
BODIPY BOron-DIPYrromethene IE expression Immediate early expression
BP2000 Black Pearls 2000 (electrode) LEDs Light emitted diodes
Br2TPCorrH3 5,15-Bis-(2,6-dibromophenyl)- MALDI/TOF Matrix assisted laser desorption
10-phenylcorrole ionization/time of flight
Br8TPFCorrH3 2,3,7,8,12,13,17,18-Octabromo- MES buffer 2-(N-Morpholino)ethanesulfonic
5,10,15-tris-pentafluorophenyl- acid buffer
corrole MOF Metal organic framework
CD CycloDextrin MPXV MonkeyPoX Virus (Class 3)
CNS Central nervous system MRI Magnetic resonance imaging
CNTs Carbon nanotubes MWCNTs Multi-walled carbon nanotubes
COFs Covalent organic frameworks NaTFPB Sodium tetrakis[3,5-bis(trifluoro-
CT-DNA Circulating tumor deoxyribonu- methyl)phenyl]borate
cleic acid NaTPB Sodium tetraphenylborate
DAFPCorrH3 5,15-Bis-(4-aminophenyl)-10- NIR Near-infrared
pentafluorophenylcorrole o-NPOE 2-Nitrophenyl octyl ether
DFT/TDDFT Density functional theory/time- OAT Oxygen atom transfer
dependent density functional OER Oxygen evolution reaction
theory OMCorrH3 2,3,7,8,12,13,17,18-Octamethyl-
DMF Dimethylformamide corrole
DMHECorrH3 7,13-Dimethyl-2,3,8,12,17,18- ORR Oxygen reduction reaction
hexaethylcorrole pAldDPFCorrH3 5,15-Bis-pentafluorophenyl-10-
5,15-DN-10oMCorrH3 5,15-Bis-(4-nitrophenyl)-10-(2- (4-formylphenyl)corrole
methoxycarbonylphenyl)corrole PC71BM [6,6]-Phenyl C71 butyric acid
5,15-D(4-NH2Ph)10-FPCorrH3 5,15-Bis-(4-aminophenyl)-10- methyl ester
(pentafluorophenyl) corrole PCA Principal component analysis

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PCE Power conversion efficiency T(4-NH2P)CorrH3 5,10,15-Tris-(4-aminophenyl)-

PDI Photodynamic inactivation corrole
PDT Photodynamic therapy TNPCorrH3 5,10,15-tris-(4-nitrophenyl)-
PET Photoinduced electron transfer corrole
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PET Positron emission tomography TOF Turnover frequency

pfu Plaque-forming units TPFCorrH3 5,10,15-Tris-pentafluorophenyl-
10-PhDPFCorrH3 5,15-Bis-pentafluorophenyl-10- corrole
phenylcorrole TPCorrH3 5,10,15-Triphenylcorrole
Photofrin Porfimer sodium (photosensiti- TpCPCorrH3 5,10,15-Tris-(4-carboxyphenyl)-
zer used in PDT) corrole
PK/PD Pharmacokinetic/ TpMCPCorrH3 5,10,15-Tris-(4-carboxymethyl-
pharmacodynamic phenyl)corrole
PMMA Polymethylmetacrylate TPPH2 5,10,15,20-Tetraphenyl-
PSA Polar surface area porphyrin
PTB7 Poly[[4,8-bis[(2-ethylhexyl)oxy]- p-TsOH para-Toluenesulfonic acid
benzo[1,2-b:4,5-b 0 ]dithiophene- TtBuPCorrH3 5,10,15-Tris-(4-tert-butylphenyl)-
2,6-diyl][3-fluoro-2-[(2-ethylhexyl)- corrole
carbonyl]thieno[3,4-b]thiophene- TTCorrH3 5,10,15-Tris-(4-methylphenyl)-
diyl]] (polymer used in solar cells) corrole
PVC Poly(vinyl chloride) VARV VARiola Virus (Class 4)
PVDF Polyvinylidene fluoride VOCs Volatile organic compounds
10-pyrDFPCorr 5,15-Bis-pentafluorophenyl-10-
pyrenyl-corrole
QMBs Quartz crystal microbalances Conflicts of interest
ROS Reactive oxygen species There are no conflicts to declare.
SAR Structure–activity relationship
SAW Surface acoustic wave (sensor)
SEM Scanning electron microscope Acknowledgements
SPECT Single photon emission com-
puted tomography CDN gratefully acknowledges the support from Italian INAIL
spyro-OMeTAD 2,2 0 ,7,7 0 -Tetrakis[N,N-di(4- (project Bric2019-ID7), the EU (Horizon2020 Project IMPAQT).
methoxyphenyl)amino]-9,9 0 - CG gratefully acknowledges support from the CNRS (UMR
spirobifluorene UB-CNRS 6302), the Université Bourgogne Franche-Comté,
TACNMe3 1,4,7-Trimethyl-1,4,7- UBFC, the Conseil Régional de Bourgogne through the Plan
triazacyclononane d’Actions Régional pour l’Innovation (PARI II CDEA), the European
TBHP tert-Butyl-hydroperoxide Union through the PO FEDERFSE Bourgogne 2014/2020 and the
TCF3PCorrH3 5,15-Diphenyl-10-(4- CoMICS (Chemistry of Molecular Interaction Catalysis and Sen-
trifluoromethylphenyl)corrole sors) program, the ISITE CO2DECIN (ANR-15-IDEX-0003, UBFC).
TDMACl Tributylphosphate and tridodecyl The French Research Agency (ANR) is also greatly acknowledged
methyl-l ammonium chloride for financial supports (AAPG 2015, ANR-15-CE04-0008, CO3SENS
TECorrH3 5,10,15-Tris-(ethoxycarbonyl)- project) and (AAPG 2020, ANR-20-CE39-0016-01, MIPEnz-
corrole Decontam project). RP gratefully acknowledges support from the
TFA Trifluoroacetic acid Italian MUR (SUNSET PRIN2017 project #2017EKCS35), the Uni-
TFMCorrH3 5,10,15-Tris-(trifluoromethyl)- versity of Rome Tor Vergata (SensAir project E81I18000180005), the
corrole EU (Horizon2020 FET-OPEN project INITIO).
T(2,6-Cl2)PCorrH3 5,10,15-Tris-(2,6-dichlorophenyl)-
corrole References
T(2,6-F2)PCorrH3 5,10,15-Tris-(2,6-difluorophenyl)-
corrole 1 A. W. Johnson and I. T. Kay, J. Chem. Soc., 1965, 1620, DOI:
TmCPCorrH3 5,10,15-Tris-(3-carboxyphenyl)- 10.1039/jr9650001620.
corrole 2 The Porphyrin Handbook, ed. K. M. Kadish, K. M. Smith and
TMesCorrH3 5,15-Bis-mesityl,10-(2,4,6-tris- R. Guilard, Academic Press, Amsterdam, 2003, pp. xxvii–
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