Metal Corrole

Coordination Chemistry Reviews 388 (2019) 360–405
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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr
Review
Metal complexes of corrole

Sara Nardis, Federica Mandoj, Manuela Stefanelli, Roberto Paolesse ⇑
Department of Chemical Science and Technologies, University ‘‘Tor Vergata”, Rome, Italy
a r t i c l e i n f o a b s t r a c t
Article history: The coordination chemistry of corrole is one of the most intriguing aspects of this contracted porphyri-
Received 28 December 2018 noid, for both theoretical and practical reasons. Corrole, in fact, shows a remarkable coordinative versa-
Received in revised form 26 February 2019 tility, and several elements have been coordinated in formally high oxidation states, because of its
Accepted 27 February 2019
trianionic character as ligand and the high electron density. These features, however, prompt corrole
to show a non innocent ligand character, making difficult to elucidate the electronic structure of the
Dedicated to Professor Armando J.L. corresponding complexes. These characteristics make corrole complexes of interest for a wide range of
Pombeiro for his outstanding achievements application fields, going from catalysis to chemical sensors. The important progresses in the synthetic
in Coordination Chemistry and Catalysis. pathways of this macrocycle have also been an important factor to widen the ‘‘periodic table” of
metallocorroles, which is now large as much as that of the corresponding metalloporphyrins. All these
Keywords: features make corrole one of the most popular macrocycle in the porphyrinoids field. This is confirmed
Porphyrinoids by the impressive number of the published articles related to metal complexes of corrole in the
Metallocorroles 2016–2018 period, which is the focus of this review.
Non innocent ligand
Ó 2019 Elsevier B.V. All rights reserved.
Nitrogen ligands
Catalysis
Energy conversion
Photodynamic therapy
Chemical sensors
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
1.1. Metallocorroles synthesis and functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
1.1.1. Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
1.1.2. 3d transition metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Abbreviations: corr, corrole; tpcorr, 5,10,5-triphenylcorrole; tfpcorr, 5,10,15-tris(pentafluorophenyl)corrole; ttcorr, 5,10,5-tritolylcorrole; tpomepcorr, 5,10,15-tris(4-
methoxyphenyl)corrole; ttppcorr, tris(2,4,6-triphenyl)phenylcorrole; tpXpcorr, 5,10,15-tris(para-X-phenyl)corrole; 5,10-bfpcorr, 5,10-bis(pentafluorophenyl)corrole; 5,15-
bfpcorr, 5,15-bis(pentafluorophenyl)corrole; tpfcorrCN, 5,15-bis(pentafluorophenyl)-10-(4-cyanophenyl)corrole; 5,15-dm-10omepcorr, 5,15-dimesityl-10-(4-methoxyphe
nyl)-corrole; 5,15-dm-10Xnpcorr, 5,15-dimesityl-10-(3-nitro,4-X-phenyl)corrole; 5,15-dnp-10Xnpcorr, 5,15-bis(4-nitrophenyl)-10-(3-nitro,4-X-phenyl)corrole; 5,15-bpfp-
10cpcorr, 5,15-bis-pentafluorophenyl-10-(4-carboxymethylphenyl)corrole; 5,15-bpfp-10tmsecorr, 5,15-bis(pentafluorophenyl)-10-(trimethylsilylethynyl)corrole; 5,15-bcp-
10-pfpcorr, 5,15-bis-(4-carboxymethylphenyl)-10-pentafluorophenylcorrole; 5,15-dt-10acorr, 5,15-di(4-methylphenyl)-10-(4-aminophenyl)corrole; tmcorr, 5,10,15-
trimesitylcorrole; tEtcorr, 5,10,15-tris(ethoxycarbonyl)corrole; tpfcorrSO3, 2,17-bis-sulfonato-5,10,15-tris(pentafluorophenyl)corrole; TAcorr, 5,10,15-tris(4-aminophenyl)
corrole; Br14Tm,m0 MeOPcorr, 2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(20 ,60 -dibromo-30 ,50 -dimethoxyphenyl)corrole; I8TpCNPCorr, 2,3,7,8,12,13,17,18-octaiodo-5,10,15-
(40 -cyanophenyl)corrole; tFcorr, 5,10,15-tris(trifluoromethyl) corrole; tFccorr, 5,10,15-triferrocenylcorrole; tbupcorr, 5,10,15-tris(4-tert-butylphenyl)corrole; ttfsppycorr,
5,10,15-tris[2,3,5,6-tetrafluoro-4-(1-methylpyridinium-4-sulfanyl)phenyl]corrole; ttfsopycorr, 10,15-tris[2,3,5,6-tetrafluoro-4-(1-methylpyridinium-2-sulfanyl)phenyl]cor
role; topycorr, 5,10,15-tris-(1-methylpyridinium-2-yl)corrole; hedmcorr, 2,3,8,12,17,18-hexaethyl-7,13-dimethyl-corrole; tpps, 5,10,15,20-tetrasulfonatophenyl porphyrin;
tpyMePI, 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin tetraiodide; tomeppor, 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin; oep, octaethylporphyrin; tpp,
5,10,15,20-tetraphenylporphyrin; tbuppor, 5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrin; tpyMePI, 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin tetra-iodide;
CV, cyclic voltammetry; DFT, density functional theory; Tp, tris(pyrazolyl)borate; THF, tetrahydrofuran; CNTs, carbon nanotubes; Cp, cyclopentadienide; Tp, tris(pyrazolyl)
borate one; 3-DMA, 3-(dimethylamino)acrolein; PE, phenylethynyl; TFA, trifluoroacetic acid; HER, hydrogen evolution reaction; OER, oxygen evolution reaction; ORR, oxygen
reduction reaction; NIPU, non-isocyanate polyurethane; WOR, water oxidation reactions; TEA, triethylamine; TP, terphenyl; RDE, rotating disk electrode; RRDE, rotating ring-
disk electrode; EPPG, edge-plane pyrolytic graphite; HAT, hydrogen atom transfer; 2,4-DTBP, 2,4-di-tert-butylphenol; PU, polyurethane; TBAB, tetrabutylammonium
bromide; PPNX, bis(triphenylphosphoranylidene)ammonium halide; PACorr, corrole functionalized poly-acrolein microspheres; PDT, photodynamic therapy; ROS, Reactive
Oxygen Species; PDI, photodynamic inactivation; QCM, quartz crystal microbalances; VOC, volatile organic compounds; hiPSCs, human induced pluripotent stem cells.
⇑ Corresponding author.
https://doi.org/10.1016/j.ccr.2019.02.034
0010-8545/Ó 2019 Elsevier B.V. All rights reserved.
S. Nardis et al. / Coordination Chemistry Reviews 388 (2019) 360–405 361

1.1.5. Lantanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
1.1.6. Ferrocenylcorrole complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
1.1.7. Functionalization of metallocorroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
1.1.8. Demetallation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
2. Characterization of metallocorroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
2.1. The ligand non-innocence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
2.1.1. Iron corroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
2.1.2. Cobalt corroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
2.1.3. Manganese corroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
2.1.4. Gallium corroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
2.2. Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
2.2.1. Co corroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2.2.2. Fe triferrocenylcorroles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
2.3. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.1. Energy conversion reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.2. Hydrogen evolution reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.3. Oxygen evolution reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
3.4. Oxygen reduction reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
3.5. Solar cell applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
3.6. Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
4. Biological and medical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
4.1. Anticancer applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
4.2. Photodynamic inactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4.3. ROS decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
4.4. Chemical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
4.4.1. Oxygen sensor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
4.4.2. Sensor arrays (gas phase). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
4.4.3. Sensor arrays (liquid phase). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.4.4. Ion selective electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.5. Deposition of metallocorroles on surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1. Introduction For this reason this review has been divided in different sections,
starting from the synthesis and going to the corrole applications.
The corrole chemistry has witnessed an impressive boost in the Free base or corrole analogous are out of the scope of this review.
first two decades of the new century, and this tumultuous growth
coincides with the definition of simple synthetic methods for the 1.1. Metallocorroles synthesis and functionalization
preparation of the corrole free bases [1]. The better availability of
the starting ligand, in fact, has allowed the preparation of a series Nowadays, the list of the metals coordinated to the corrole ring
of corrole metal complexes, with a significant expansion of the so- is very rich, showing for corrole a coordinative versatility that can
called Periodic Table of Metallocorroles. compete with the more famous porphyrin and phthalocyanine
This expansion has been beneficial for the elucidation of differ- rings; however, the preparation of new metallocorroles still
ent peculiarities of metallocorroles, which make them different remains a field of increasing interest for the researchers since the
from analogous complexes of porphyrins, and consequently peculiar and unique features of this contracted ligand.
increasing their interest for both theoretical and practical reasons. In the last two years, some more positions of the ‘‘periodic
As an example, the frequent non innocent character of corrole as table” of metallocorroles have been filled, welcoming new compo-
ligand makes the behaviour of the corresponding metal complexes nents, such as Silicon [3,4], Technetium [5], Tantalum [6], Cerium
peculiar and their catalytic activity important for applications of and Lutetium [7]; novel synthetic strategies, for example for Plat-
interest. inum [8] and Manganese [9] insertion, have been finely tuned
The consequence of both the synthetic availability and the com- and a significant number of functionalized corrole complexes have
prehension of the metallocorrole properties is the seminal been reported, to satisfy the requirements needed to cope with dif-
exploitation of metallocorroles in different fields, ranging from ferent application fields, ranging from catalysis through antitumor
medicine to chemical sensors. therapeutics to optical sensors.
This huge number of corrole related research articles motivated
also the publication of different reviews focused on different topics 1.1.1. Silicon
of this macrocycle, with the most recent published in a thematic The previous examples of Silicon coordinated to a corrole like
collection a couple of years ago [2]; in this manuscript we want analogous present in literature is related to the corrolazine deriva-
to review the further developments related to the preparation, tives, obtained by the ring contraction of the corresponding silicon
characterization and application of corrole metal complexes, cov- tetrabenzophthalocyanine [10]. Quite recently, two different
ering in large part the last two years, with the aim to provide an groups reported almost simultaneously two synthetic routes for
update on the different aspects of the chemistry of metallocorroles. the preparation of silicon complexes of several corroles, highlight-
362 S. Nardis et al. / Coordination Chemistry Reviews 388 (2019) 360–405
Scheme 1. Synthesis of Si(IV) corrole and preparation of the corresponding l-oxo dimer.
Scheme 2. Si-complexes obtained from aryl- and alkylcorroles.
ing the intriguing optical and electrochemical properties of these sion characterized by high quantum yields, which makes them
species. Osuka and coworkers have isolated [3], in good yields, Si particularly intriguing as optical sensing material. In this view,
(IV) corrole complexes by reaction of different meso-aryl substi- the high affinity of Si for the fluoride ion was demonstrated in solu-
tuted corroles with tetrachlorosilane in 1,2-dichloroethane at tion, and a Si-corrole paper-based optode was realized, with
60 °C, in the presence of N,N-diisopropylethylamine. Furthermore, promising possibility to be applied as naked eye detector for fluo-
the reaction of the tfpcorrSiOH derivative with methanesulfonyl ride, as shown in Fig. 1 [4].
chloride in pyridine, at 100 °C, gave the corresponding m-oxo dimer
(Scheme 1).
Alternatively, Paolesse and coworkers [4] have reacted ttcorr 1.1.2. 3d transition metals
with Si2Cl6 in pyridine, obtaining, within one hour, two fractions, A recent green synthetic route for the preparation of Mn(III)
corresponding to the monomeric and the l-oxo dimer Si com- derivatives of corrole has been developed [9]. Generally, man-
plexes respectively. Besides, they have noticed that the peripheral ganese corroles are synthesized by reaction of the free base with
substituents of the corrole ring strongly influence the nature of the Mn(II) acetate in polar solvents [11], while in this approach man-
metalation products. With b-alkyl corroles, a l-oxo dimer is the ganese initiates the cyclization of bilane through carbon-carbon
main product, whereas a hydroxo complex is obtained when bond formation, to yield Mn(III) corroles under aerobic conditions
electron-withdrawing substituents are present, as in the case of (Scheme 3). Since it is valid for any type of substituted aldehyde
tfpcorr (Scheme 2). and aryldipyrromethane, this method presents a general nature
In both articles, the authors highlight the very good photophys- and avoids the crucial step to form firstly the CAC bond of the
ical properties of the complexes, with intense fluorescence emis- dipyrrin and the subsequent cyclization as reported in literature.
are stable and exhibit remarkable chemical and photophysical

properties, which explain their interest as oxygen sensors, photo-
sensitizers in PDT and dye-sensitized solar cells [14–16]. Quite sur-
prisingly, significant gaps remain in the literature of 4d
metallocorroles. For example niobium, technetium and palladium
corroles were essentially unknown until 2016, and synthetic routes
to mononuclear ruthenium corroles remained poorly developed
[17]. In this last two years period, Ghosh’s group has given a signif-
icant contribution in this regard. Firstly they reported the synthesis
of a series of complexes, with the general formula [tpXpcorr]99Tc
(O) (X = CF3, H, Me, and OMe), using 99Tc(I) compound (NEt4)2[-
fac-99TcCl3(CO)3] as the 99Tc source and they afford the highly
stable 99TcO corroles (Scheme 5), in reasonably good yields (15–
51%) [5].
Of the four complexes synthesized, a single-crystal X-ray struc-
ture has been determined for tpomepcorr99Tc(O), revealing geo-
metrical parameters nearly identical to those of the
corresponding ReO complex (Fig. 2). However, a significant spec-
Fig. 1. Colorimetric variation of ttcorrSi solutions in presence of different anions
(top) and of ttcorrSi spotted on paper strips (bottom) on exposure to fluoride tral shift between the Soret maxima of TcO (410–413 nm) and
solutions. a) 102 b) 103 c) 104 d) 105 e) 106 mol L1 f) blank. Adapted with ReO (438–441 nm) corroles was observed, and in particular the
permission from Ref. [4]. Copyright 2018 Wiley. Soret maxima of Tc complexes have been shown insensitive to
the para-substituent X, with a red shift of just 3 nm going from
X = CF3 to X = OCH3, indicating, as reported in the following sec-
tion, an innocent character of corrole in the complex. These syn-
thetic routes potentially pave the way toward 99Tc-porphyrinoid-
based radiopharmaceuticals.
Subsequently the same group reported a modified synthetic
protocol to prepare monomeric Ru corrole complexes, based on
the interaction of free-base corroles, [Ru(COD)Cl2]2, and nitrite in
refluxing 2-methoxyethanol; this has been shown to provide reli-
able access to two new families of ruthenium triarylcorroles,
[tpXpcorr]Ru(NO) and [tpXpcorr]RuVI(N) [18]. Importantly, they
found that RuNO corroles undergo thermally induced deoxygena-
tion to yield Ru(VI)N corroles, the first ruthenium(VI) derivatives
Scheme 3. Synthesis of diverse Mn(III) corroles by two different routes (a and b).
of corroles (Scheme 6).
The new complexes have shed light on periodic trends and rel-
ativistic effects for group 8 metallocorroles. Corrole acts as inno-
The new A2B Mn(III)-corroles were synthesized in good yield for
cent ligand in the nitrosyl Ru complexes, as suggested by both
different applications.
theoretical and spectroscopic characterization, different from the
Two articles have been recently published reporting a new and
corresponding iron derivatives. The synthetic pathway allows the
facile photochemical entry to produce and study high-valent
preparation of monomeric Ru corrole complexes, opening the
corrole-Mn(V)-oxo derivatives by photolysis induced upon visible
way for their potential applications in different fields.
light irradiation of the corresponding Mn(IV) bromate or nitrite
Bröring and coworkers have prepared the so-called ‘‘Viking hel-
complexes (Scheme 4) [12,13]. Mn(V)-oxo corroles have been
met” corroles, by reacting oxido Mo corroles with SiCl4 to obtain
obtained by light induced oxidation from the OABr or OAN bond
the corresponding dichlorides [19]. These complexes have called
splitting, as confirmed by kinetic and UV-visible behaviors.
Viking helmet because of the distorted trigonal prismatic coordina-
tion geometry, with the chloride ligands on the same side of the
1.1.3. 4d transition metals distorted corrole ring. This approach allows the activation of the
The coordination of the second and third row transition metals otherwise inert Oxido Mo Corroles, with the formation of
to corroles represents a challenging task, because of the contracted organometallic derivatives by the substitution of the axial chlo-
inner core cavity of the macrocycle. Despite a steric mismatch rides. Following this approach it has been reported the preparation
inherent in their structures, the majority of 5d metallocorroles of a corrolocene complex, by reaction of the Viking helmet Mo
Scheme 4. Photochemical production of corrole-Mn(V)-oxo complexes from the corresponding Mn (IV) nitrite complexes by visible light irradiation.
99
Scheme 5. General procedure for the preparation of TcO corroles.
reaction of a free-base corrole and Pt4(OAc)82HOAc in benzonitrile

at high temperature.
Another structural characterization of a 5d group corrole has
been reported by Arnold and coworkers; Tantalum corroles have
been obtained via alkane elimination, from trialkyl tantalum pre-
cursors, upon reaction with the free base corrole 5,15-tmp-
10omepcorr [6]. The crystal structure of the dichloride tantalum
corrole showed a domed conformation of the corrole ring, with
the Ta ion out of the macrocyclic plane and the two chloride
ligands displaced in the same side of the complex (Fig. 5).
From the dichloride tantalum corrole they were able to synthe-
size and isolate a dimethyl derivative, which has comparable reac-
tivity toward CO as a dimethyl tantalum porphyrin cation, but
leads to a considerably less stable enediolate product (Scheme 8).
The imido tantalum corrole can be protonated by triphenyl-
methanol to form an alkoxide-amido species, while protonation
by 4-methylbenzyl alcohol results in a bis(alkoxide) species and
the release of tBuNH2 (Scheme 9).
1.1.5. Lantanides
Considering the interest in corrole coordination chemistry, it is
Fig. 2. X-ray crystal structure of tpomepcorr99Tc(O): a) front view, b) side view.
remarkable that f-element corrole synthesis is still considerably
Reprinted with permission from Ref. [5]. Copyright 2016 Wiley.
underdeveloped [21–23]. Lanthanides, on the other hand, have
been used to great effect in single molecule magnets and for bio-
corrole with sodium cyclopentadienide. The X-ray structure of the logical imaging, due to their low toxicity and unique electronic
complex (Fig. 3) shows a domed conformation of the corrole ring, properties [24]. To expand the diversity of lanthanide corrole coor-
with the Mo ion out of the macrocycle plane toward the cyclopen- dination chemistry, the design of cerium corroles with anionic cap-
tadienide ring, with an average distance in the expected value for a ping ligands has been reported; in particular two different anions,
Mo(IV) ion. the Cp one (left pathway in Scheme 10) and the Tp (right pathway
in Scheme 10), were exploited [7].
A polymer, with the general formula [5,15-dm-10-omepcorrCe
1.1.4. 5d transition metals (THF)–CpNa]n, is formed using NaCp and a dimeric structure, with
The synthesis of the first set of stable Pt(IV) complexes has been the general formula (5,15-dm-10omepcorrCeATp)2, is formed
defined, by addition of pyridine to the reaction mixture obtained at when KTp is used (Scheme 10). Encapsulation of the counter-
the end of the Pt insertion (Scheme 7) [8]. cation leads to the isolation of the monomeric structures, with
These complexes have the general formula [tpXpcorr]PtIV(m/p- the general formulas [AM(2.2.2-cryptand)][5,15-dm-10-omepcorr
C6H4CN)(py), where X = CF3, H, and CH3. The X-ray crystal structure CeACpAX] (AM = Na or K, X = Cp or Tp). Besides, the authors high-
of these complexes showed the presence of the Pt ion in the plane lighted how the encapsulation of the counter ion has a larger
of corrole ring, as showed for the [tpXpcorr]PtIV(m-C6H4CN)(py) impact on the electronic structure of such molecules than
structure reported in Fig. 4. expected.
Platinum(IV) corroles have been previously reported by the
same group [20], showing a particularly intriguing axial reactivity. 1.1.6. Ferrocenylcorrole complexes
In the previous work, however, they were accessible via a low It has been demonstrated that corrole in many cases can act as a
yielding, serendipitously discovered reaction, which involved the non innocent ligand and undergoes an internal electron transfer
Scheme 6. Synthetic procedure for the preparation of ruthenium corroles.
exhibit strong ligand-to-metal electronic communication. In this

regard, the macrocycle functionalization with ferrocenyl periph-
eral substituents could be of particular interest, since Fc is not only
a good electron-donating substituent, but also an electro-active
group, whose oxidation potential may be affected by interaction
with the metallocorrole counterpart. In this regard, Paolesse group
has reported the synthesis and characterization of different iron
tFccorr, bearing NO, r-Ph or Cl as axial ligands [26]. The tFccorr-
FeCl was synthesized by direct metalation of the crude product
obtained by the reaction of ferrocenyl aldehyde with pyrrole,
avoiding the need to isolate the unstable free-base corrole, as ear-
lier reported for structurally related Cu and Co derivatives [27]. The
isolated tFccorrFeCl was then subjected to axial ligand exchange,
leading to the generation of the diamagnetic tFccorrFeNO and the
paramagnetic tFccorrFePh derivatives (Scheme 11).
The synthetic and functional importance of the ferrocenyl sub-
stituent in the corrole chemistry, has been highlighted also by Kar
and coworkers, which presented a remarkable procedure to con-
vert a porphyrin into a corrole ring, with quantitative yields [28].
The authors have synthetized two different A2B2-ferrocenyl-
porphyrins, following a modified synthetic protocol; subsequently,
they have reacted the corresponding free-base porphyrins with
copper acetate and silver acetate respectively, in presence of an
excess of triethylamine (Scheme 12). Surprisingly, with the copper
salt they got novel porphyrin complexes, while with silver salt they
Fig. 3. X-ray crystal structure of the Mo corrole complex. Reprinted with permis- observed the formation, through ring contraction, of the corre-
sion from Ref. [19]. Copyright 2017 Wiley. sponding silver complexes of corrole.
between the conjugated p system and the central metal ion [25]. 1.1.7. Functionalization of metallocorroles
Generally, to study this corrole feature, two types of metal com- The corrole properties can also be modulated by suitable
plexes are investigated, the copper and the iron ones, since they peripheral modifications, as widely demonstrated in these last
Scheme 7. Synthesis of stable Pt(IV) corroles.
Fig. 5. X-ray crystal structure of 5,15-tmp-10omepcorrTaCl2. Reprinted with

permission from Ref. [6]. Copyright 2017 Royal Society of Chemistry.
The bromo-copper complexes have been demetalated, under

reductive conditions, affording the free base corrole ligands, which
in turn have been readily complexed with Mn(III) and Au(III) ions
Fig. 4. X-ray crystal structure of the [tpXpcorr]PtIV(m/p-C6H4CN)(py) complexes. (Scheme 13).
Reprinted with permission from Ref. [8]. Copyright 2018 American Chemical
Alternatively, Gross and coworkers reported the iodination
Society.
reaction with NIS, but using a (tpfcorr)Co as substrate; it is note-
worthy that in this case the corrole complex undergoes a partial
two years by both Ghosh [29–31] and Gross [32–34] groups. In substitution of the b-pyrrolic positions, affording (tpfcorr-I3)Co
detail, Ghosh and coworkers have focused their attention on the and (tpfcorr-I4)Co in 30% and 61% yields, respectively, while
halogenation reactions; careful choice of starting materials and (tpfcorr-I2)Co was prepared via the stepwise synthesis, similar to
proper reaction conditions has allowed them to synthesize novel previous reports for iodo-substituted copper, silver and gold cor-
copper corrole structures such as (Br14Tm,m0 meopcorr)Cu [29] roles (Scheme 14).
and (I8tpcnpcorr)Cu [30], by using the common procedures based Starting from this new protocol based on the one-pot metala-
on molecular bromine or N-iodosuccinimide, respectively. tion/iodination reaction, the authors have also developed a proce-
The X-ray structure of (I8tpcnpcorr)Cu (Fig. 6) showed a dure to replace the halogens with CF3 groups.
strongly saddled distortion of the corrole ring, which was however The utility of a ‘‘ACF3” precursor for replacing the iodine atoms
similar to that reported for the analogous b-octabromo-complex. via nucleophilic substitution was found to be best for the gold
sulfonation has been very useful for the preparation of amphiphilic

corroles and, before this paper, it had been successfully applied
only to a single corrole derivative: the tfpcorr [36].
A more generic approach to modify the electronic and spectro-
scopic features of corrole derivatives is to tune or extend their p
system; that can be realized both extending the conjugation of
the corrole by the fusion with aromatic rings and introducing
one or more conjugated functional groups on the peripheral posi-
tions. In this scenario, two recent contributions of the Paolesse
group have to be mentioned. In a first article [37] they reported
the preparation of b,b0 -pyrazino-fused corroles, starting from the
copper complex of 2-amino-3-nitro-tbupcorr in order to use the
amino group as starting point for the synthesis of the pyrrole moi-
ety via a Clauson-Kaas reaction. Subsequently, once reduced the
nitro group with 10% Pd/C-NaBH4, the complex was reacted with
p-tolualdehyde, following the Pictet-Spengler route reported for
the analogous Ni porphyrin and affording novel p-extended b,b0 -
Scheme 8. Synthesis of dichloride, dimethyl and enediolate tantalum corroles. pyrrolo(1,2-a)pyrazino-fused corroles (Scheme 16).
A useful reaction for the functionalization of the corrole ring is
the Vilsmeier-Haack reaction, which has been exploited in the past
corrole, while very low yields were obtained for copper and silver for the introduction of formyl group at the peripheral position of
complexes. Investigation of the 2,3,17,18-tetra-CF3- and 2,3,17- the macrocycle [38]. Using the same reaction protocol, the func-
tris-CF3-substituted-corrolato gold(III) complexes has shown that tionalization of ttcorrCoPPh3 by the introduction of acrolein groups
the introduction of these groups has immense effects on the struc- has been obtained [39]. The reaction was done by reacting the 3-
tures of the complexes, their photophysical and redox properties, DMA/POCl3 mixture as Vilsmeier reagent with ttcorrCoPPh3 in a
and on their catalytic performances. On the basis of these results, dichloromethane solution. The resulting 3-acrolein corrole com-
Gross and coworkers have also reported a successful approach plex was obtained in high yields; by changing the reaction condi-
for the synthesis of tpfcorr by using pyrrole and halothane (4:3 tions, the 3,17-disubstituted complex can be obtained, although
ratio), with sodium dithionite as radical initiator [34]. Besides, they in lower yields. The regioselectivity of the reaction was confirmed
analysed their chelating ability by introducing gallium, manganese by the X-ray crystallographic characterization of both complexes
and phosphorus, because of their biomedical and catalytic proper- (Fig. 7).
ties respectively. It is interesting to note that the corrole functionalization
As just mentioned above, the peripheral functionalization of induced a significant modification of the visible spectra, with an
corroles has seen playing a key role in the auration reaction; in a evident red shift and increase of the intensity of the Q bands
similar, but opposite way, Paolesse and coworkers have demon- (Fig. 8).
strated how the insertion of phosphorus into the macrocycle is cru- The same reaction was later exploited with Copper and Gallium
cial for the sulfonation of corroles [35]. In details, they reported a complexes (Scheme 17) [40]. It is interesting to note that both the
novel and regioselective strategy for the synthesis of a water sol- metal coordinated to the corrole ring and the number of acrolein
uble phosphorus corrole complex, in an almost quantitative yield units strongly influence the yields and the optical properties of
(Scheme 15). This represent a very important result because the the products.
Scheme 9. Synthesis of the imido tantalum complex and its reactivity upon treatment with alcohols.
Scheme 10. Synthesis of [5,15-dm-10-omepcorrCe(THF)–CpNa]n and (5,15-dm-10omepcorrCe–Tp)2. Adapted with permission from Ref. [7]. Copyright 2016 Royal Society of
Chemistry.
Scheme 11. Preparation of different tFccorrFe complexes.

Scheme 12. Different reactivity of A2B2-ferrocenyl-porphyrins with copper acetate and silver acetate.
led to the desired corroles 3,17-bis-PE-tpcorrCu and 3,17-bis-PE-

ttcorrCu (Scheme 18). The octa-PE derivatives were synthesized
using appropriate amounts of the octabromocorrole and n-tributyl
phenylethynylstannane in 1,4-dioxane at 75 °C for 1 h, with Pd
(PPh3)4 as a catalyst (Scheme 18). In all cases the addition of PE
groups to the b-pyrrole positions of the corrole results in dramatic
red shifts in the electronic absorption spectra and new reductions
processes.
A different approach for the extension of the p-electronic cor-
role structure has been recently reported by two different authors,
Di Gao [42] and Haas [43] respectively. The first work is based on
the study and characterization of four new phosphorus(V) 5,15-
diester corroles, obtained by reaction of the corresponding free
base with POCl3 in pyridine (Scheme 19).
The strong electron-withdrawing character of 5,15-ester groups
was demonstrated and it even exceeds that of pentafluorophenyl
groups. This efficiency probably results from the low steric hin-
drance of ester moieties, which allows a good p overlap with the
aromatic system of the macrocycle. Indeed, the nature of the
remaining meso substituent tunes the physicochemical properties
of these phosphorus complexes only slightly, but unexpectedly
plays a key role in the ruffling of the structure (Fig. 9).
Schöfberger and coworkers have reported a novel synthetic
procedure to obtain the 5,15-bpfp-10tmsecorr, otherwise not
accessible via standard procedure, by reacting 2 eq. of dipyrro-
methane, 1 eq. of trimethylsilylpropynal, and 0.5 mol% TFA (based
on dipyrromethane) at 20 °C [43]. The desired product was
obtained in 10% yield and subsequently used as substrate for a
Fig. 6. X-ray crystal structure of (I8tpcnpcorr)Cu; a) front view, b) side view.
further functionalization via sila-Sonogashira-cross-coupling with
Reprinted with permission from Ref. [30]. Copyright 2018 American Chemical
Society. 1-iodopyrene, under ambient conditions, in presence of a common
catalyst system and Cu(OAc)2 (Scheme 20). This functionalization
Kadish and coworkers synthesized di- and octa-PE substituted procedure leads to an A2B corrole and the corresponding copper
p-extended copper corroles [41]. The di-PE substituted ones were complex, characterized by an extended p-electronic structure at
synthesized via a Stille coupling reaction followed by demetalla- meso-position 10, which reveals strong changes in the UV-Vis spec-
tion to give the free base di-PE derivatives. Cu metallation then tral region.
Scheme 13. Synthesis of halogenated copper corrole complexes.
Based on the Sonogashira-cross-coupling reaction, it has been alation approaches have been recently proposed [51,52]. In the
reported the synthesis of meso-meso linked ethynyl-bridged first work [51] it has been observed that in a series of Ag(III) com-
porphyrin-corrole dyads and triads, which represent a promising plexes, the treatment with methyl magnesium chloride resulted in
approach for the preparation of p-extended electronic system, the formation of the corresponding free base corroles in excellent
allowing to fuse and emphasize the promising properties of differ- yields. This procedure, compared to the previously ones reported,
ent macrocycles [44]. improved significantly the yields and produced exclusively the cor-
In this scenario, recently, Osuka and coworkers reported the responding free base corroles, without b-substitution of the
successful synthesis of two types of meso-free corroles, namely macrocycle.
5,10-bfpcorr and 5,15-bfpcorr, via rational synthetic routes, and On the other hand, it has been shown how copper undecaaryl-
investigated their reactivities at the free meso-positions through corroles can undergo a facile acid-induced demetalation, in a mat-
oxidative dimerization and meso-halogenations [45–49]. The opti- ter of minutes, under both reductive and nonreductive conditions
cal and electrochemical properties of all the synthesized corrole [52]. However, in the first case the resulting free base proved to
derivatives have been studied and revealed significant electronic be light- and oxygen-sensitive, readily oxidizing to open-chain
effects, depending upon the substitution positions and hence upon dioxotetrapyrroles and 5/10-OH isocorroles. Instead, the use of
the positions of meso-meso linkage for the dimeric species, in addi- nonreductive conditions led to 50–75% yields of undecaarylisocor-
tion to the axial ligand coordination modes. roles, whose interaction with gold(III) acetate resulted in a rearom-
atization of the macrocycle affording the corresponding gold
1.1.8. Demetallation undecaarylcorrole complex.
As well as the metalation and functionalization reactions are
decisive for fine-tuning the corrole features, a key role is played 2. Characterization of metallocorroles
by the demetalation procedures. In fact, in porphyrin chemistry,
various functionalizations at the meso- and b-positions of the 2.1. The ligand non-innocence
macrocycles are often carried out by selective metalation and
demetalation reactions. Contrary to porphyrin-based systems, the One of the most intriguing and challenging features of corrole is
development of suitable demetalation strategies for corrole chem- related to the characterization of its coordination chemistry. Cor-
istry is still in its infancy [50]. In this regard, two different demet- role is in fact a trianionic ligand with a contracted core and for this
Scheme 14. Iodination reaction of (tpfcorr)Co.
reason the coordinated metals usually show formal oxidation roles. The redshift of the Soret band was in fact observed for the
states higher than the corresponding metalloporphyrin complexes. series of corrFeCl, corrFeNO and [corrFe]2O complexes (Fig. 10),
However the definition of the exact electronic configuration of while no substantial changes were observed for corrFeAr deriva-
these complexes is complicated by the frequent non innocent tives, where corrole essentially acts as innocent ligand.
ligand character of corrole [53], which usually makes difficult to In the same work, the authors investigated also the application
assign the real oxidation state to the coordinated metal. Since of the K-edge X-ray absorption near-edge spectroscopy (XANES)
the beginning of corrole chemistry this ambiguity induced to some for the characterization of corrole innocence in the series of Iron
incorrect characterization of corrole complexes [54], with the most complexes tpcorrFeCl, tpcorrFe(NO), (tpcorrFe)2O and tpcorrFePh.
evident debates in the case of iron complexes [55]. The electronic The spectroscopic data obtained were combined with TDDFT calcu-
structures of corrole complexes have been recently reviewed by lations for tpcorrFeCl and tpcorrFePh, gave useful insights to estab-
Ghosh [25], and in these last two years his group has given an lish the noninnocence of corrole in the corresponding complexes.
important contribution reinvestigating the behaviour of complexes On the other hand, redox data were not useful to probe the ligand
already known, such as those of Co and Fe, and giving some spec- nature in the case of iron corroles, because the redox potentials, for
troscopic tools that can be generally used to characterize the coor- both the first oxidation and reduction processes, showed no differ-
dination behaviour of corrole and its innocent or non innocent ences among innocent and non innocent complexes.
character as ligand. A similar pattern has been observed in the case of a similar ser-
ies of tFccorrFe complexes (Scheme 21) [26]. In this case the elec-
tronic configuration of the complexes has been investigated by
2.1.1. Iron corroles both 1H and 13C NMR spectroscopy. The spectra of all the species
They started from well characterized Fe corroles to test the effi- have been fully assigned by recording COSY, NOESY, HSQC and
ciency of different spectroscopic data as probes to elucidate the HMQC spectra. The electronic behaviour of the complexes is simi-
non innocent character of corrole as ligand [56]. In Iron complexes, lar to that of the previously reported iron tritolylcorroles [57], with
in fact, corrole has been characterized as non innocent ligand for the FeCl showing the more pronounced non innocent character and
corrFeCl, corrFeNO and [corrFe]2O, while almost innocent in the with the Fe-Ph having only a slight radical character in the corrole
corrFePh derivative. Ghosh demonstrated that optical spectroscopy ring.
is very useful to individuate the noninnocence of corrole, because
in this case a meso aryl to ligand charge transfer process leads to
a systematic bathochromic shift of the Soret-like band upon 2.1.2. Cobalt corroles
increasing electron donating character of the meso substituent, Novel insights on the electronic configuration of corrCo pyri-
while these spectral changes are absent for innocent metallocor- dine complexes have been recently reported [58]. CorrCo(py)2
Scheme 15. Regioselective strategy for the preparation of a water soluble phosphorus corrole complex.
complexes are well known diamagnetic derivatives, with a labile influenced by the peripheral meso aryl substituents, showing red
character of the axial pyridine ligands, which dissociate in solution shifts with the increasing electron donating character of the sub-
to give the corresponding penta-coordinated species. stituents on the meso aryl groups. This feature was absent in the
The optical spectra of a series of meso-phenyl substituted corrCo UV-visible spectra of the corresponding Rh corrole complexes.
complexes (Fig. 11), showed systematic red shifts for the corrCo These results indicate that corrole is non innocent in the case of
(py) complexes, which were absent for the corresponding hexaco- Cobalt complexes, which can be formulated as (corrole2)Co(II),
ordinated species, readily obtained by addition of pyridine in the with the two radicals antiferromagnetically coupled to give the
solution. apparent diamagnetic complex. Rh corrole complexes are on the
These results suggested that the CorrCo(py)2 complexes were other hand innocent species, formulated as (corrole3)Rh(III). This
effectively innocent Co(III) derivatives, while the electronic config- confirms that second-row transition metal complexes are usually
uration for the pentacoordinated species was better formulated as innocent complexes. The optical features of octabrominated cor-
(corrole2)Co(II). DFT calculations supported the non innocent for- role Co complexes showed also in this case the absence of the influ-
mulation for the pentacoordinated complex, with a metal(dz2)- ence of the meso aryl substituents, but this result is due to the lack
corrole a2u orbital interaction, which is similar to that indicated of conjugation between meso aryl rings and the corrole macrocycle,
for other pentacoordinated corrole complexes of first-row transi- due to steric hindrance. These formulations were also supported by
tion metals, such as Mn, Fe and Cu [25]. DFT calculations, while more complex data were obtained from X-
The corresponding octabrominated corrCo(py) complexes did ray spectroscopy: while XAS spectra indicated a lower charge in
not show similar redshifts in the optical spectra, but in this case the case of Co corrole to respect the corresponding tppCo(III)Cl,
this result is not due to an innocent character of the corrole, but in the case of emission X-ray spectroscopy, no differences were
to the lack of the aryl-to-corrole charge transfer interaction, pre- observed. This result was attributed to higher covalent character
vented by the steric hindrance of the peripheral bromine atoms, of the metal ligand interaction in the case of corrole complexes.
which did not allow conjugation of the meso aryl substituents to
the corrole ring. Also in this case redox data were not useful to 2.1.3. Manganese corroles
probe the noninnocence of corrole, while EPR clearly showed sim- Mn corroles have also been investigated; although these com-
ilar broad signal for all the pentacoordinated species. plexes have been synthesized several years ago and widely used
The results obtained seem to indicate that the non innocence of for catalytic applications [60], the investigation of their electronic
corrole is quite common for the first-row transition metal com- configurations has not been detailed like that of the analogous Fe
plexes of corrole. To further study this aspect, Ghosh and co- derivatives. Using the same successful approach described for the
workers investigated the electronic structures of the Co and Rh previous studies, Ghosh’s group studied in detail the electronic
triphenylphosphine corrole complexes [59]. Also in this case, the configuration of a different corrMnCl and corrMnPh complexes
Soret-like band position of the Co complexes was significantly (Scheme 22) [61].
Scheme 16. Synthesis of p-extended b,b0 -pyrrolo(1,2-a)pyrazino-fused corroles.
Fig. 7. X-ray crystal structure of: a) 3-acrolein-ttcorrCoPPh3 and b) 3,17-bis-acrolein-ttcorrCoPPh3. Reprinted with permission from Ref. [39]. Copyright 2017 Wiley.
The series of corrMnCl complexes showed significant batho- plex, the first example of non innocent corrole complex with a
chromic shifts depending on the electron donating nature of the main group metal. These species (Scheme 23) were prepared by
peripheral meso-aryl group, once again suggesting the non inno- oxidation of the tfpcorrGa complexes with the Magic Blue oxidant,
cent character of corrole in these complexes. The corresponding and the structural characterization showed a chloride ion coordi-
corrMnPh series showed spectra insensitive to the peripheral sub- nated to the axial position of the Ga centre.
stitution, indicating in this case an essential innocent character of The complex was almost planar, with only slight distortions
the corrole ligand. DFT calculations and XANES spectroscopy sug- (Fig. 12). This result indicated that the metal(dz2)-corrole a2u orbi-
gested an antiferromagnetically coupled (corrole2) Mn(III) for- tal interaction, which leads to the macrocycle distortion observed
mulation for corrMnCl and an essentially (corrole3)Mn(IV) in the case of transition metals, has a stabilizing effect, but it is
configuration for corrMnPh. not essential to stabilize non innocent corrole complexes.
2.1.4. Gallium corroles 2.2. Electrochemistry

A different example of noninnocence of corrole has been
reported [62]; while the example of non innocent complexes has Electrochemistry has been a useful tool to characterize the com-
been reported with coordinated transition metal ions, Sankar and plex redox behavior of corrole complexes, taking in account also
coworkers reported a full-fledged non innocent Ga corrole com- the non innocent character of such a macrocycle [63].
Fig. 8. UV-vis absorption spectra in CH2Cl2 of 3-acrolein-ttcorrCoPPh3 (solid line), 3,17-bis-acrolein-ttcorrCoPPh3 (dotted line), ttcorrCoPPh3 (solid-dotted line). Reprinted
with permission Ref. [39]. Copyright 2017 Wiley.
2.2.1. Co corroles The first reduction of tmcorrCo in CH2Cl2 occurred at a potential

Kadish and co-workers have recently studied the influence of b- identical to that of analogous Cu complex, confirming the above
nitro substituents on the redox processes of Cu corroles in different described non innocent character of corrole and ruling out the pre-
solvents [64]. Cu corroles are now a well recognized example of a vious hypothesis of a Co(III)/Co(II) metal centred redox process.
non innocent corrole complex, formulated as (corrole2)Cu(II) The first oxidation is metal centred, producing the cationic species
complex and the first reduction of this neutral complex afford [(corrole2)Co(III)]+, confirmed by the visible spectrum of this spe-
the corresponding anion (corrole3)Cu(II), with the reduction of cies, which shows reduced intensities for both Soret and Q bands
the radical macrocycle. b-Nitro corroles did not show a different and broad band over 600 nm.
pattern in the solvents considered, while a peculiar difference to When 2 equivalents of pyridine are present in CH2Cl2 solution,
respect of unsubstituted complexes was observed in the case of the Co corrole binds a pyridine to form the pentacoordinated spe-
the second reduction, which occurs at lower potentials for the nitro cies, also in this case formulated as [(corrole2)Co(II)](py). The first
derivatives. Spectroelectrochemistry indicated that this redox pro- reduction shows a large separation among the cathodic and the
cess occurred at the metal centre, supporting the formation of a subsequent anodic reoxidation peak, indicating the loss of the axial
(corrole3)Cu(I) derivative, which is not possible in the case of pyridine upon reduction. The first oxidation process is metal cen-
unsubstituted Cu corrole complexes. tred also for the pentacoordinated species, forming the [(cor-
Nitrophenyl substituted corroles have also been studied in the role2)Co(III)]+(py) species, which can then coordinate a further
case of Cobalt derivatives, starting with the hexacoordinated bis- pyridine to form the hexacoordinated complex. In neat pyridine,
pyridine species [65]. The redox behaviour of 5,15-dm- the hexacoordinated species is formulated as a innocent complex,
10XnpcorrCo(py)2 (X = F, OCH3) and 5,15-dnp-10XnpcorrCo(py)2 and the first reduction is metal centred giving the [(corrole2)Co
were compared with that of the corresponding four coordinated, (II)](py), upon dissociation of one pyridine ligand.
unsubstituted tmcorrCo complex, as shown in Scheme 24. In the case of nitro substituted corrCo complexes, the redox
As earlier observed in the case of Cobalt b-octaalkylcorroles behaviour is essentially similar to that observed for the unsubsti-
[66], also for the nitrosubstituted Co corroles the coordinated pyr- tuted species, with the addition of the waves of the electroactive
idine ligands are labile in CH2Cl2 and PhCN, as indicated by the nitro phenyl groups. A difference can be however observed for
changes of the visible spectra, which are also concentration depen- the corrole 5,15-dnp-10XnpcorrCo(py)2 (X = F, OCH3), having three
dent, due to the presence of the dissociation equilibrium: nitrophenyl substituents; in this case the first reduction did not
induce the loss of one axial pyridine ligand, and the process gener-
corrCoðpyÞ2 ¢corrCoðpyÞ þ py ates the stable [(corrole2)Co(II)](py) species, as evidenced by the
The redox behaviour of these complexes is quite complicated, almost reversible wave in the Cyclic Voltammogram.
because Cobalt ion can assume different oxidation states when The electrochemistry of the same structural Co corroles, but
coordinated to the corrole ring, from Co(I) to Co(IV), offering differ- bearing DMSO as axial ligand, has been characterized by the same
ent possible metal and macrocycle centred redox processes, with authors [67]. For all these complexes the axial ligand dissociates in
the scheme even more complicated by the dissociation of axial pyr- highly diluted CH2Cl2 solutions (105 M), giving the tetracoordi-
idine in CH2Cl2 of PhCN. Furthermore, the influence of peripheral nated species. In more concentrated solutions (103 M) the tetra-
nitrophenyl substituents can also change the site of the electron coordinated species is present for tmcorrCo, while the others
transfer. To obtain insights on the electrochemistry of such a spe- retain the axial DMSO. Finally, in neat DMSO, the five coordinated
cies, the authors started from the characterization of the four coor- complex is present for tmcorrCo, 5,15-dm-10XnpcorrCo (X = F,
dinated, unsubstituted tmcorrCo in CH2Cl2, CH2Cl2 with 2 py OCH3), while an equilibrium between penta- and hexacoordinated
equivalents and in neat pyridine. derivatives occurs for 5,15-dnp-10XnpcorrCo (X = F, OCH3), having
Scheme 17. Acrolein-ttcorr Cu and Ga complexes.
Scheme 18. Di- and octa-PE substituted p-extended copper corroles.

Scheme 19. Synthetic protocol for the preparation of phosphorous(V) 5,15-diester corroles.
Fig. 9. a) Representation of the ruffling torsion angle W and b) side view of X-ray crystal structure of phosphorus(V) 5,15-diester corroles. Adapted with permission from Ref.
[42]. Copyright 2017 Wiley.
Scheme 20. Synthesis of an A2B corrole with an extended p -electronic structure at meso-position 10.
three nitrophenyl substituents. The redox behaviour of these com- viour of Co corroles in solution: the dissociation of the axial ligands
plexes resembles that of the previously studied py derivatives, was in fact easier for corroles bearing electron releasing sub-
with the axial DMSO involved in the different processes, as stituents on the meso aryl groups, while the presence of electron
reported in Scheme 25 for tmcorrCo complex. CV ran under CO withdrawing species favoured the formation of hexacoordinated
atmosphere confirmed the ability of corrCo to bind CO as axial species. Also in this case the redox behaviour of these Co corroles
ligand in CH2Cl2, resulting in shifts of both 1st oxidation and reduc- was complicated by the lability of the axial ligands, in particular
tion, to respect the same processes done under N2. CO is lost both in the case of ammonia, where both tetra-, penta- and hexa-
upon reduction and oxidation, showing a binding constant one coordinated species can be present in solution.
order of magnitude lower than that of DMSO.
The same authors reported a further work on corrCo derivatives, 2.2.2. Fe triferrocenylcorroles
in this case studying the behaviour of bis-ammonia and DMSO The electrochemistry of three tFccorrFe complexes has been
complexes of some Co corroles (Scheme 26) [68]. Ammonia coordi- investigated, with the interest related to the presence in these
nation leads to the formation of the corresponding hexa- complexes of iron centres in different oxidation states [26]. For this
coordinated species, which easily dissociates to the corresponding reason, the behaviour of three different iron corrole complexes, the
tetracoordinated complex, an important intermediate as receptor diamagnetic tFccorrFeNO and the paramagnetic tFccorrCl, where
for CO detection in SAW sensors [69]. the corrole is non innocent, and the tFccorrFePh complex, where
The spectroscopic characterization of these complexes demon- the corrole is reported as partially innocent, have been character-
strated that the meso aryl groups influence the coordinative beha- ized. Furthermore, the meso-ferrocenyl groups are also electroac-
Fig. 10. UV-vis spectra of corrFeCl, corrFeNO and [corrFe]2O complexes evidencing a redshift of the Soret band. No substantial changes were observed for corrFeAr derivatives
Reprinted with permission from Ref. [56]. Copyright 2017 Wiley.
tive substituents, and they can give three oxidation processes, in [(corrole3)Fe(IV)]Ph were quite similar, spectroelectrochemistry
addition to the corrole and Fe centred redox pathways. The three confirmed the different electronic configurations of the two
one electron oxidations of the meso-ferrocenyl groups are well sep- complexes.
arated, when the CV was carried out using TBA[B(C6F5)4] as sup-
porting electrolyte in PhCN, showing similar potentials for the 2.3. Optical properties
three Fe complexes.
Although the electronic configurations of the nitrosyl and r- One of the most interesting features of corroles are related to
phenyl complexes are different, represented as [(corrole2)Fe(II)] their excellent optical properties, such as higher fluorescence
NO and [(corrole3)Fe(IV)]Ph, they show two reversible reductions quantum yields than porphyrins and phosphorescence emission
and one oxidation at very similar potentials, while the [(corrole2) for some metal complexes [25]. These properties make them spe-
Fe(III)]Cl has a completely different redox behaviour, as reported cies promising for application in different fields, ranging from
in Scheme 27. Although the CVs of [(corrole2)Fe(II)]NO and chemical sensors [70] to PDT applications [71]. For this reason, it
Scheme 21. Structures of iron tFccorr with different axial ligands.
Fig. 11. Optical spectra of a series of meso-phenyl p-substituted corrCo complexes. (a) tFcorrCo(py)2, (b) tpXpcorrCo(py)2 series in CH2Cl2, (c) tpXpcorrCo(py)2 series in CH2Cl2
with 0.5% pyridine, (d) Br8tFcorrCo(py)2, (e) Br8tpXpcorrCo(py)2 series in CH2Cl2, (f) Br8tpXpcorrCo(py)2 series in CH2Cl2 with 0.5% pyridine. Reprinted with permission from
Ref. [58]. Copyright 2017 American Chemical Society.
irradiation, the EPR of the solution were registered in the presence

of spin trapping reagents (Fig. 13).
In the presence of the reagent TEMP, which generates TEMPO
upon reaction with singlet oxygen, its typical EPR signal pattern
was obtained, with a larger intensity in the case of tpfcorrGa(py),
confirming the efficient 1O2 generation by this species, different
from tpfcorrSO3Ga. This corrole generated the EPR spectrum of
DMPO-OH species when irradiated in the presence of the spin trap-
ping reagent DMPO, indicating the generation of the OH radical by
electron transfer from corrole to O2. The ability of the OH radical to
damage DNA can be responsible of the PDT action of this corrole.
Finally, imaging measurements in vitro demonstrated that the
water soluble Ga corrole was accumulated in human prostate car-
cinoma cancer cells, confirming its promising properties for PDT
application.
In the PDT field, the singlet oxygen generation is a crucial pro-
cess and for this reason the generation of excited triplet state by
intersystem crossing is of fundamental importance. To have infor-
mation on the influence of coordinated metals or the corrole ring
Scheme 22. Different MnCl and MnPh corrole complexes.
substitution by heavy atoms on the triplet state generation, the
excited states dynamics of (tpfcorr)SbF2 [73] and Ga and Al iodi-
is of paramount importance to characterize the photophysical nated corrole complexes [74] have been studied in detail.
properties of metallocorroles. From this point of view, the photo- The dynamics of the excited states for the Sb corrole showed the
physical characterization of a water soluble tpfcorrSO3Ga has been direct Soret fluorescence emission around 430 nm, violating the
carried out, comparing its behaviour with that of the correspond- Kasha rule, in the femtosecond region. In the picosecond delay
ing tpfcorrGa(py) in different organic solvents, with the aim to give time, the fluorescence of Q bands, in the 570–700 nm region was
useful insights on the activity of this complex as anti-cancer drugs observed, generated by the Soret-Q band internal conversion. At
under physiological conditions [72]. The absorption spectrum of longer scale time, the intersystem crossing occurred, with an
tpfcorrSO3Ga in TRIS HCl solution showed reduced intensities of almost unitary quantum yield and the consequent fluorescence
both Soret and Q bands to respect the corresponding spectra of decay. The high quantum yield supported an efficient spin orbit
Ga corroles in organic solvent, together with an evident red shift coupling due to the coordinated Sb ion.
of the Q bands for the water soluble corrole. The reduced intensity When the fluoride axial ligands of a Sb corrole complex are sub-
of absorption bands can be related to the solvent polarity, as sup- stituted with chloride or bromide ligands [75], both fluorescence
ported by a similar reduction observed for tpfcorrGa(py) in metha- quantum yields and lifetimes significantly decrease in the order
nol and ethanol. A similar feature is present for fluorescence chloride-bromide, indicating a more efficient spin-orbit coupling
emission, although the quantum yield of the water soluble Ga cor- with the heavier bromine atoms. The axial ligands are photo-
role complex is still significantly higher than that of the corre- labiles and they undergo photolysis giving the corresponding Sb
sponding tpps. Femtosecond Transient Absorption spectra (III) complex upon irradiation both in the UV and in the visible
showed longer lifetime for the triplet state of Ga water soluble cor- region.
role than those of tpfcorrGa(py) in the organic solvents. The inter- The introduction of halogen atoms on the peripheral positions
action of these complexes with O2 was also strongly influenced by of the corrole ring demonstrated to induce the intersystem cross-
the solvent. While tpfcorrGa(py) generates singlet oxygen with a ing populating the lowest Q triplet state, with a resulting quench-
0.43 quantum yields in toluene, the corresponding value for the ing of the fluorescence emission and generation of
water soluble corrole was too weak to be detected. To investigate phosphorescence emission in Al, Ga and P tpfcorr [76]. The excited
in deeper detail the interaction with molecular oxygen upon state dynamics of Ga and Al iodinated tpfcorr, with iodine number
Scheme 23. Species obtained by oxidation of tfpcorrGa complexes with the Magic Blue oxidant.
3. Applications
3.1. Energy conversion reactions
The access to varied and formally high oxidation states for coor-
dinated metals in several corrole complexes warrants the exten-
sive investigation of this macrocycle in catalysis, with a
particular attention to relevant reactions for energy conversion
[77]. Among the various complexes, the Co derivatives have been
largely studied, revealing to be extremely versatile catalysts in
HER, OER and ORR reactions, where they assume variable valency
forms, from +1 and +3 or more in the former two processes and +2
in the latter. In this section, we report the recent advances on the
development of corrole complexes in these reactions, mostly
focusing the discussion on the Co corroles, which resulted the
undisputed protagonist in this field.
3.2. Hydrogen evolution reaction
The production of hydrogen gas from electrocatalytic water

splitting is a highly pursued process to replace fossil fuels and to
move towards sustainable and environmentally friendly energy
sources. Some Pt-based systems catalyse H2 evolution from water,
Fig. 12. X-ray crystal structure of the full-fledged non innocent Ga corrole complex:
a) front view, b) side view. Reprinted with permission from Ref. [62]. Copyright but both their rarity and high cost make them far from to be sus-
2017 Wiley. tainable resources. In this scenario, the development of HER cata-
lysts made of inexpensive and earth-abundant metals represents
a challenge, where metallocorroles are gaining ground. The more
recent literature describes the possibility to enhance the HER activ-
varying from 0 to 4 (Scheme 28), have been investigated to obtain ity of metallocorroles mainly by a rational modulation of the elec-
information on the mechanism of the ‘‘heavy atom effect” on the trochemical features, by changing the molecular structures with
intersystem crossing process. proper substituents or metal coordinated and/or by immobilizing
The study revealed that the introduction of iodine atoms on the the molecular catalysts onto different substrates. As just reported,
b -positions of the corrole ring increases the intersystem crossing Co corroles display superior electrocatalytic activity compared to
rate according to the halogen atoms. In this case the coordinated other metal complexes, which is generally due to the formation
metal has no significant influence and no important differences of a Co(I) species as a hydride active intermediate, able to react
have been observed among Al and Ga complexes, because the with H+ and release H2 according to the pathway depicted in
metal orbitals do not mix with those of the macrocycle. On the Scheme 29.
contrary, iodine atoms generate charge transfer states, facilitating Liang and coworkers investigated the possibility to generate
the Soret – Q internal conversion and the intersystem crossing by novel HER catalysts finely modulating the corrole skeleton proper-
spin orbit coupling. This study shed light on the multiple pathway ties in varied Cu(III) and Co(III) trans-A2B corrole complexes. Since
affecting the dynamics of the corrole photophysical processes, the introduction of electron-withdrawing substituents at the
which can be extended to different aromatic compounds. macrocycle periphery leads to a lowered electron density on the
Scheme 24. Structures of 5,15-dm-10XnpcorrCo(py)2 (X = F, OCH3), 5,15-dnp-10XnpcorrCo(py)2 and unsubstituted tmcorrCo complexes used for the redox behavior
comparison.
whose activities can be finely controlled by combining the electron

density of the meso-aryl rings, the best results are achieved with
strongly electron-withdrawing substituents in all the meso-
positions rather than electron-donating groups at the B-phenyl
unit.
Concurrently, they reported a similar study centred on the
seven Co(III)PPh3 A2B-triarylcorroles reported in Scheme 30, evi-
dencing a two-steps modulation of electrocatalysed HER by these
complexes, with the 5,15-dnp-10tfpcorrCo(PPh3) showing the
highest catalytic efficiency [80]. The introduction of F atoms onto
the corrole peripheral positions represents a viable strategy to
increase the efficiency of a HER catalysts, but others can be
exploited. In this respect, Cao and coworkers reported recently a
detailed study demonstrating both the role of the axial ligand on
Scheme 25. Redox processes for corrCo(DMSO) complexes. Co corrole complexes and the influence of a pyrenyl unit inserted
on a meso-position on the electrocatalytic ability of these deriva-
tives for H2 evolution in pH 0–14 aqueous solutions, when
macrocyclic system, making corrole significantly easier to reduce adsorbed on graphene [81]. They investigated the two corrCo com-
and more difficult to oxidize, the authors studied the effect of plexes with the pyrenyl group on C10 reported in Scheme 31, first
halogenation at the C10-positions of different 5,15-dinitroph studying their electrocatalytic behaviour in acetonitrile using ben-
enylcorroles on the catalytic activity in proton reduction reactions. zoic acid as the H+ source. The A3-triarylcorrole tpfcorrCo(py)2 was
In a first paper [78], they prepared and provided the optical and also considered to value the effect of the aromatic unit inserted on
redox properties of four copper complexes of the corroles 5,15- the ability to catalyse the proton reduction.
dnp-10pcorr, 5,15-dnp-10Fpcorr, 5,15-dnp-10F2pcorr, 5,15-dnp- Although the reaction mechanisms of HER was found similar for
10tfpcorr reported in Scheme 30 by using optical spectroscopy, the three complexes, involving the two electron-reduced forms of
electrochemistry and spectroelectrochemistry, together with DFT the Co-corroles, the catalytic activity was found different, being
theoretical calculations. All the collected data proved Cu(III) com- higher for the tpfcorrpyrCo(PPh3) complex than for the analogous
plexes as potential good catalysts and this finding was also sup- with pyridine. This result confirms the trans effect on the hydrogen
ported by the kinetic reactivity and onset potentials measured evolution reactions: having PPh3 a higher electron density if com-
during the experiments. Indeed, catalytic waves emerged when pared with pyridine, it favors the electrophilic attack of H+ toward
TFA was added to homogeneous benzonitrile solutions at poten- the trans position of the metal centre. For the same ligand (py), the
tials close to the Cu(III)/Cu(II) redox couple of the tested com- larger catalytic currents were observed for tpfcorrCo(py)2, easier to
plexes. A clear enhancement in the kinetic reactivity was found reduce to give the catalytic active species. The same compounds
by increasing the number of AF atoms at the B-phenyl position. were immobilized on graphene (G) and the nanocomposite mate-
Moreover, testing different concentrations of TFA, a direct evalua- rials were fully characterized by several spectroscopic techniques,
tion of catalytic efficiency between all the copper corrole deriva- to confirm the graphene functionalization and highlight the nature
tives was possible and revealed the complex containing the of the noncovalent interactions between the two components. As
higher number of fluorine atoms as the most efficient one. The expected, the introduction of pyrenyl group favours the adhesion
same authors investigated also how the introduction of electron of corroles onto graphene, thanks to strong p-p interactions, gen-
donating groups at the B-phenyl position to give the Cu(III) com- erating robust catalysts with improved catalytic efficiency, due to
plexes of 5,15-dnp-10dmapcorr, 5,15-dnp-10omepcorr, 5,15-dnp- the ease of electron transfer between the electrode surface and
10tFpcorr and 5,15-dnp-10(tF)2pcorr having push-pull properties the composite material. The catalytic activities of the composites
can influence the catalytic activity of the corresponding complexes in both acidic and basic solutions (pH range of 0–14) have been
[79]. Although all the complexes resulted as efficient HER catalysts, tested, showing the following catalytic HER activity trend: tpfcor-
Scheme 26. corrCo derivatives used to study the behaviour of bis-ammonia and DMSO complexes.
Scheme 27. Redox processes of [corrol2Fe(III)]Cl.
[82]. For this aim, they prepared carbon-based hybrid materials

where CNTs were functionalized with Co corrole derivatives by
both covalent and supramolecular approaches. In the first case
the 10-azidophenyl corrole tpfcorrazCo(py)2 (Scheme 31) was
attached on alkyne-functionalized CNTs with either short conju-
gated groups or long alkane chains by ‘‘click” reactions, giving
the hybrids H1 and H2, respectively. Collecting different experi-
mental evidences, including cyclic voltammetry, FTIR spec-
troscopy, EDX, XPS and TEM microscopy, the authors concluded
that the azidocorrole was homogeneously immobilized on carbon
surface, maintaining intact its molecular structure. Otherwise,
the deposition of corroles tpfcorrpyrCo(py)2 and tpfcorrCo(py)2
gave the hybrids H3 and H4, respectively, and occurred through
the strong p-p interactions of these electron-rich macrocycles,
which was remarkable for the pyrenyl functionalized corrole. The
cobalt content has been measured for the four hybrid systems,
being essential for the comparison of the catalytic activities for
all the materials investigated. Although Co corroles exhibited the
same redox and catalytic behaviour, showing the same molecular
natures when performed OER and HER reactions in organic sol-
Fig. 13. EPR spectra of Ga corroles upon light irradiation, in the presence of spin vents, with a trend of tpfcorrCo(py)2 > tpfcorrpyrCo(py)2 > tpfcor-
trapping reagents. Adapted with modification from Ref. [72]. Copyright 2017
razCo(py)2, all the corresponding hybrid systems resulted active
American Chemical Society.
for H2 and O2 evolution at pH 7, following a reverse order:
rpyrCo(PPh3)/G > tpfcorrpyrCo(py)2/G > tpfcorrCo(py)2/G. We can
H1 >> H3 > H2 H4
summarize the novelty of this work in the use of the pyrenyl unit
to improve the immobilization of corroles onto the graphene sup- The importance of catalyst immobilization on the overall elec-
port, as well as the facilitation of electron transfer between the two trocatalytic performance was clearly demonstrated. The hybrid
materials; moreover, the crucial role of the axial ligand bearing by H1 was found to be remarkably active as molecular OER and HER
the Co atom on the HER ability was also clearly pointed out. catalyst in neutral solutions, having onset overpotentials of 450
The investigation on the effects of immobilization methods on and 430 mV for OER and HER, respectively. Both values are consid-
catalytic activity was very recently reported by the same authors erably smaller than the typical values with Hangman and with
Scheme 28. Aluminum and Gallium tpfcorr with iodine number varying from 0 to 4.
Scheme 29. General mechanistic pathway for HER electrocatalysed by Co corroles.
Scheme 30. Molecular structures of metallocorroles investigated by Liang and coworkers [78–80].
non-supported Co corroles. Moreover, this hybrid system worked An electron-deficient cobalt corrole complex has been tested by
and was very stable also in strong acidic and basic conditions, so Zhan and coworkers as an electro- and photochemical catalyst for
being an OER and HER catalyst in pH 0–14 aqueous solutions. the H2 evolution from water, used as proton source, which repre-
The covalent attachment onto CNT surface by a rigid and conju- sents a very intriguing medium to obtain hydrogen gas in a sus-
gated linker avoids the corrole degradation (demetallation and/or tainable manner [83]. In details, the tEtcorrCo bearing two
oxidative dimerization processes), stabilizing the active Co(I) and pyridine molecules as axial ligands was synthesized and its elec-
Co(V) intermediates onto electrode surface during the reaction at trocatalytic activity was determined in DMF, with acetic acid as
electrochemical timescales. Furthermore, experimental and theo- the proton source, and in water. A higher TOF value at lower over-
retical studies rationalized the different activities found for the potential in water than to the organic medium was obtained. The
four hybrids as different electron transfer efficiencies between Co homogeneous catalytic system developed was proven to be stable
complexes and carbon nanotubes, resulting from a different molec- and robust, showing mainly linear charge build-up over time,
ular arrangement onto the surface. without losing activity within 3 days. The authors provided the
Scheme 31. Molecular structures of cobalt pyrenyl functionalized triarylcorroles investigated by Cao and coworkers [81,82] in HERs.
use of the prepared tEtcorrCo as a photocatalyst for HER from with other catalysts previously reported, this system possesses
water, using [Ru(bpy)3]Cl2 as photosensitizer, combined with similar parameters to the octafluoro Co corrole reported by Gross
ascorbic acid as the sacrificial electron donor species. The opti- [85] in terms of TON and overpotentials, but higher TOF values
mization of conditions identified pH = 4.5 as the best pH value and mildest acidic environment required.
for the H2 generation, upon continuous irradiation with a light-
emitting diode lamp (k = 469 nm) of a 0.25 M buffer solution, in 3.3. Oxygen evolution reaction
the presence of different concentrations of the corrole catalyst,
spanning in the 2.28–6.84 M range. The mechanism for this The O2 generation from electrocatalytic water oxidation is a
photo-induced production of molecular hydrogen is the following: desired process, but hard to accomplish for both thermodynamic
2þ 2þ and kinetic reasons. Indeed, the reaction proceeds much slower
RuðbpyÞ3 ! RuðbpyÞ3 than the HER and largely limits the overall efficiency of water split-
ting systems. In this context, metallocorroles have been shown to
2þ þ
RuðbpyÞ3 þ AA ! RuðbpyÞ3 þ AAþ be highly active, bringing to O2 evolution from H2O via the mech-
anistic pathway illustrated in the case of cobalt complexes and
þ 2þ generally valid for the monomolecular catalysts (Scheme 32).
RuðbpyÞ3 þ H2 O ! 0:5H2 þ OH þ RuðbpyÞ3 Two water molecules are involved for the generation of one oxygen
The catalyst concentration was found to influence the photo- molecule. The first step consists in the addition of H2O to the cat-
generation of hydrogen. Indeed, after 3 h of irradiation a remark- alytic centre with the formation of a hydroxyl adduct through
able increasing of TON value from 92 to 152 was measured as proton-coupled electron transfer. This species further evolves in a
the Co-corrole concentration was lowered from 6.84 to 2.28 M. metal-oxo intermediate which undergoes to the nucleophilic
Further, the photocatalytic activity of the complex is not affected attack of a second molecule of water to give the metal-
by the air, giving the same amount of evolved H2 under argon hydroperoxide complex. The last step is the further oxidation lead-
atmosphere as well as aerobic conditions. ing to a dioxygen adduct on the metal centre that finally releases
The photogeneration of hydrogen from water reduction by iron O2. It is important to note that there is a significant presence of
and cobalt corroles was also recently reported by Doctorovich et al. high-valent metal intermediates in the depicted cycle, therefore
[84]. The authors discussed the efficiency of corrole complexes dif- the current research aimed to develop metallocorrole catalysts to
ferently substituted on the meso-positions to produce H2 both in efficiently generate O2 from water is readily warranted.
homogeneous environment and adsorbing a Co(III) 5,10,15-tris(4- Recently, Cao and co-workers deeply explored how the modifi-
nitrophenyl)corrole onto carbon nanotubes. In the first case, where cation of Co corrole molecular structure can influence the catalytic
the catalysts were dissolved in dioxane and TEA and TP were used performances in water oxidation reactions. In a first work, they
as the sacrificial donor and the sensitizer, respectively, the mass of showed how the secondary coordination sphere of the examined
H2 produced was found quite similar for all the complexes tested, complexes is a significant aspect to take into consideration for
as well as the TOF and TON values. Indeed, the very negative the catalyst design [86]. In details, they prepared and fully charac-
potential of TP sensitizer is able to reduce all the corroles indepen- terized four cobalt corroles with a dibenzofuran unit functionalized
dently by their redox potentials, thus the TOF measured is quite a with different appended acid/base groups at the 10-position
global value accounting for the whole electron-donor properties of (Scheme 33), which are found to be in proximity of the corrole
the metallocorrole/photosensitizer system. However, the influence platform by structural studies. Although the structural differences
of substitution on the catalytic behaviour of three different Co cor- do not significantly alter the redox potentials of the complexes, the
roles was evidenced in similar experiments, where no TP was used. basicity of the appended groups remarkable affects their catalytic
In this case, the performance of the catalyst was strictly related to activity, being directly involved in making easier the O-O bond for-
the ability of the Co corrole to absorb radiation from the lamp, mation. Indeed, the OER activity measured in 0.1 M pH 7 phos-
which was higher when electron-withdrawing groups, as ANO2, phate buffers by depositing the Co corroles (20 nmol cm2) on
were located at macrocycle periphery. Although the photocatalytic fluorine-doped tin oxide (FTO) working electrodes followed the
activity in solution was relatively low, it was increased by adsorb- order:
ing the best catalyst Co(III) 5,10,15-tris(4-nitrophenyl)corrole onto
LCH2POðOHÞ2 - Co > LPOðOHÞ2 - Co > LCOOH - Co > LBr - Co
MWNTs, and using the nanocomposite material to generate H2 at
pH 3. With this system it was possible to obtain 1 mmol of H2 by which is consistent with the decrease of the pKa values of the
photoreduction using some picograms of catalyst. If compared peripheral acid groups, being 8.4, 7.1 and 4.2, respectively. The
Scheme 32. General mechanistic pathway for OER from water electrocatalyzed by Co corroles.
[pyridine(-py), 4-cyanopyridine (Apy-CN), 4-N,N0 -

dimethylpyridine (Apy-NMe2), 4-methoxypyridine (Apy-OMe),
1-methylimidazole (im-Me), thiophenate (Athi)]. Crystallographic
studies on complexes coordinated with Apy and ApyAOMe evi-
denced a distorted octahedral coordination environment of the
Co ion in both structures, with the two pyridine or p-OMe-
pyridine located in the axial positions. The effect of the trans axial
ligand on the OER activity was investigated by CV studies of FTO
working electrodes coated with the metallocorroles in neutral con-
ditions. It was found that the higher activity in water oxidation was
obtained for the complexes with electron-donating ligands. Indeed,
the catalytic current values at 1.68 V for the Apy-OMe, Aim-Me
and Athi ligated complexes were found 1.50, 1.43 and
1.95 mA cm2, respectively, which are remarkably higher than
the case of Apy-CN at the same potential (0.78 mA cm2). These
Scheme 33. Molecular structures of cobalt triarylcorroles functionalized with acid/ results can be easily explained considering that a ligand with a
base appended groups studied by Cao and coworkers in OERs [86]. strong electron-donating character deeply influences the stability
and reactivity of the ligand located in trans to it, weakening the
Co(V)-oxo bond in the corresponding complex and thus favouring
authors also assessed catalytic HER activity of the complexes, using the attack of H2O to the metal centre and the following catalytic
GC electrodes loaded with 70 nmol cm2 of corrolates in 0,1 M neu- steps leading to O2 evolution.
tral phosphate buffers, confirming the same trend justifiable in view Gross and co-workers carried out detailed studies aiming to
of a greater tendency to protonation at pH 7 of the ACH2PO2 3 identify the reactive intermediate species involved in WORs per-
group, which leads to higher local H+ concentration. formed by tpfcorrCo in homogeneous medium. Information on
In a contemporaneous paper, the same authors reported on the the redox states active in the catalytic process, as well as the influ-
influence of the trans axial ligand on the catalytic OER activity of ence of the axial ligand on the doubly oxidized Co complex have
Co corroles [87]. Starting from the axial-ligand free tpfcorrCo, been obtained by a set of experimental methodologies, including
they prepared six axially ligated cobalt corrolates, bearing N- and voltammetric techniques (CV and SWV), spectroelectrochemistry,
S-axial ligands with various electron donating character EPR and fluorine and proton NMR spectroscopies. Crucial aspects
emerged from these studies. Firstly, by comparing the oxidation modulation of corrole ring electrochemical properties, by introduc-
processes occurring on Co and Al(tpfcorr), the authors demon- ing meso- or b-substituents (typically halogens) or by coordinating
strated that the first oxidation of the Co complex is not metal- 1st row transition metal ions into the inner core. Once again,
centred, unaffected by the nature of axial ligands, and inert to among this series, cobalt was the greater protagonist in the elec-
H2O. Conversely, the second oxidation is substantially determined troreduction of O2, as illustrated by the more recent examples
by the metal coordinated, which has the Co(IV) character and reported in literature described below.
actively reacts with water. The higher catalytic activity observed Kadish and coworkers studied how the structural elaboration of
with increasing base concentration was mainly due to trans-OH Co triarylcorroles leading to b-substituted derivatives or cofacial
species formation. Interestingly, the authors reported the unex- dyads can affect the electrocatalytic activity of the complex for
pected formation of a Co(III)-superoxide complex, when a large the oxygen reduction. In a first paper, they prepared three cobalt
excess of TBAOH was added to aerobic solutions of tpfcorrCo. This corroles containing four b,b0 -butano substituents (Scheme 34),
finding is particularly appealing since this species is exploitable in characterizing them as their ability to reduce O2 both in acidic
oxygen reduction reactions. and basic solutions [89]. Electrochemical studies in dichloro-
A computational study exploring the global limitations of methane containing 0.1 TBAP revealed that the introduction of
molecular WOR catalysts has been carried out by Corminboeuf these electron donating groups renders the complexes easier oxi-
and co-workers [88]. They used linear free energy scaling relation- dizable and harder reducible, if compared with the corresponding
ships LFESR and volcano plots to evaluate the catalyst performance non-butano Co corroles. Cyclic and RDE voltammetries in aqueous
and limitations for OER reactions in the case of a set of metallocor- solutions containing 1.0 M HClO4 have been performed to evaluate
roles (M = Co, Ru, Ir, Rh coordinated to unsubstituted corrole) and the ORR catalytic activity of the prepared compounds. Each corrole
metalloporphyrins (M = Mn, Co, Ru, Rh embedded into a adsorbed on an EPPG disk electrode has similar RDE responses in
b-octafluoroporphyrin). The used model assumes that the oxygen air-saturated acid solution. Moreover, these experiments allowed
evolution from water proceeds by a mononuclear mechanism for the calculation of the number of electrons (n) transferred to
where a series of active intermediates are directly involved, i.e. O2 during the electrochemical process, by using the Koutecky-
*
AOH, *@O and *AOOH species. The information obtained from Levich plot. For each complex n was 2, indicating that molecular
the LFESRs for all the active intermediates have been casted into oxygen was reduced by these catalysts in a two-electron process
a volcano plot, whose shape is remarkably different from the cor- leading to H2O2 as the final product. The same results have been
responding solid-state counterpart, showing a large plateau at obtained when the electroreduction was performed at pH = 10,
the top where the overpotential is independent of the choice of cat- indicating these Co corroles as highly efficient ORR catalysts in
alyst. This plateau warrant for the high robustness of the molecular both acidic and basic conditions.
catalysts, on the other hand it hampers further reaction paths that In parallel, the authors reported similar studies on bis-cobalt
could improve their performances. face to face corroles connected by a xantene linker and on the cor-
responding mono-cobalt forms basis for comparison (Scheme 35)
[90]. Cyclic voltammetry showed that peak potentials for the cat-
3.4. Oxygen reduction reaction alytic oxygen reduction occurring at the Co corroles-coated elec-
trodes were similar for the two types of complexes, even if the
The ability showed by porphyrinoids to mimic some biological reaction performed by bis-corrole derivatives happened at more
systems in natural occurring reactions led to explore the use of negative potentials. Moreover, the potentials found for oxidation
porphyrins and corroles to catalyse the O2 reduction into H2O, an of these dyads were indicative of a scarce interaction between
important reaction for alternative energy conversion field. Indeed, the two macrocycles in their neutral form, which undergo a one-
these planar macrocycles can bind dioxygen to the metal centre at electron abstraction at a different half-wave potential. RDE and
the axial vacant coordination site, activating its further transfor- RRDE experiments showed that the studied compounds reduced
mation either via a two- or four-electrons pathway, which leads O2 to H2O2 (H2O was never observed as a product), but with a dif-
to hydrogen peroxide and water as the main products, respectively. ferent efficiency, being the calculated amount of the product 90–
It was found that the outcome of the electrocatalytic reaction 92% for the mono-Co derivatives and 100% for the bis-cobalt
depends on the metal coordinated, as well as the molecular struc- corroles.
ture of the corrole macrocycle. Thus, most studies aiming to opti- Elbaz and coworkers studied the effect of perhalogenation on
mize metallocorroles as ORR catalysts have been focused on the the b pyrrolic positions of a tpfcorrCo on the ORR catalytic activity,
evidencing singular phenomena when these halogenated com-
pounds were immobilized onto different carbon based surfaces
[91]. RRDE experiments on corroles deposited on glassy carbon
electrodes afforded the following trend for the onset potentials,
both in acidic and basic solutions: CoABr8 > CoACl8 CoAH8 > -
CoAF8, indicating that the catalytic activity of corrole decreased
with the halogen electronegativity. However, performing different
theoretical studies (DFT, vertical electron affinity and molecular
electrostatic potentials calculations) the unsubstituted corrole
resulted unexpectedly favoured, possessing a better ability to dis-
tribute the negative charge throughout the macrocycle in compar-
ison with the other halogenated reduced forms [CoAX8]. This
attribute makes easier the following steps of the reduction reac-
tion, as O2 binding/activation and subsequent electron transfer
events. When the same catalysts were absorbed onto the high sur-
face carbon material BP2000, the onset potentials increased to
0.85 V vs RHE in basic solutions, independently from the b-
Scheme 34. Molecular structures of b-b0 -tetrabutano-substituted cobalt triarylcor- halide, with the limiting current densities not identical and
roles investigated by Kadish and coworkers in oxygen reduction reactions [89]. increasing in the order of CoAH8 > CoABr8 = CoACl8 >> CoAF8.
Scheme 35. Molecular structures of the A2B mono-cobalt triarylcorroles and the corresponding bis-cobalt derivatives linked by a xantene acyl unit studied by Kadish and
coworkers in ORRs [90].
Interestingly, the carbon material used had a remarkable impact on

the reaction mechanism. Indeed, Levich equation gave the number
of electrons n transferred during the ORR close to 4, unlike the ORR
catalysis performed on GC which produced peroxide anion (n = 2).
The same group very recently reported a novel Co corrole-based
material (polyCoTAcorr) with improved catalytic activity achieved
by a controlled electropolymerisation of a CoTAcorr on carbon
electrodes [92]. The ANH2 peripheral functionalities enabled the
formation of a 3D polymeric structure via oxidative polymerization
of the corrole monomer dissolved in acetonitrile onto ITO surface,
similarly to phenylaniline-substituted porphyrins. The film forma-
tion was fully characterized using CV and electrochemical quartz
crystal microbalance, and studied in depth by FTIR-ATR spec-
troscopy. In details, these spectra were indicative of the almost
complete transformation of the ANH2 groups to higher N- Scheme 36. Molecular structure of the dpFccorrCo(PPh3) complex studied by Chen
substituted moieties, consistent with the covalent bond formation and coworkers in ORRs [94].
between the corrole monomers, which exclusively occurred
through the ortho positions on the aminophenyl rings. SEM images
showed that the polyCoTAcorr film formed a three-dimensional together confirming that Co corroles were successfully linked onto
cauliflower-like structures, where each particle derives from the GO surface, ruling out the mere physical adsorption. Electrochem-
aggregation of smaller nanoparticles with an average size of ical measurements on GO-corrCo coated on a EPPG disk electrode
30 nm. RRDE experiments has been carried out for both the pointed out that in air-saturated 0.1 M KOH solution the oxygen
CoTAcorr and its polymer in acidic as well as basic solutions, reduction process involves the transfer of four electrons over the
revealing superior ORR catalytic activity for the polyCoTAcorr in potential range of 0.2–0.0 V vs RHE, as indicated by the
every case, with the onset/half-wave potentials positively shifted Koutecky-Levich plots where n = 3.9–4.0. Interestingly, the authors
of 110 and 40 mV in 0.5 M H2SO4 and 0.1 M KOH, respectively also reported a comparison between the catalytic performances of
and an electron number n approaching 4 in basic solution. Remark- the covalent hybrid system and a physical mixture of GO and the
ably, when the electropolymerization was performed on BP2000, cobalt corrole to highlight the effect of chemical immobilization
all the electrochemical parameters increased. Finally, the catalytic of the macrocycle onto the carbon surface on the ability to elec-
performance of the polyTAcorr@BP2000 combination in basic envi- troreduce O2. It was found that this mechanical mixing was also
ronment was compared with a PGM-free commercial catalyst, giv- active for ORR, but unable to work as a four electrons catalyst, since
ing a onset potential difference below 50 mV together with a faster the estimated number of electrons (n) transferred was 2.8. The
reaction kinetics for the Co corrole-based material. PolyCoTA- same experiments performed in acidic media, afforded 2.0 as the
corr@BP2000 results the best, not pyrolyzed, ORR molecular cata- value of n, indicating for this system the exclusive formation of
lyst reported to date. H2O2 by oxygen reduction at 0.5 M H2SO4.
Another way to enhance catalytic performance for ORR is to Chen and coworkers first have introduced a novel bimetallic
support metalloporphyrinoids on varied carbon materials. Kadish corrole complex pyrolyzed on carbon black as an efficient non-
and coworkers reported a hybrid catalyst consisting of a cobalt tri- precious electrocatalyst for ORR [94]. The novelty of this work
arylcorrole covalently bound to graphene oxide (GO) surface (GO- was the exploration of a molecular structure having two distinctive
corrCo) able to efficiently reduce O2 by 2- or 4-electron reaction features virtually positive for enhancing the ORR activity, i.e. low
path depending on the pH range [93]. The functionalization molecular symmetry and two ORR-active metal centres (Fe and
occurred by the amidic bond formation between the peripheral Co) at once. Indeed, it was previously demonstrated by the same
amino group located on the 5,15-dt-10acorrCo(PPh3) and the acti- group that the original symmetry of different metalloporphyri-
vated carboxylic groups on GO. A collection of spectral and other noids before heat treatments has a great effect on the catalytic
techniques has been used to fully characterized the obtained mate- activity of the molecule, even if it is surely altered by pyrolysis.
rial, namely UV-vis, FTIR, TGA, XRD, XPS, AFM and TEM, all In addition, the potentialities of Fe- and Co-based systems in ORR
is broadly reported. The investigated molecule, reported in

Scheme 36, consisted of a Co 5,15-diphenylcorrole bearing a fer-
rocene unit at the 10-position, which has been prepared in an over-
all 1.5% yield following literature procedures and fully
characterized. X-ray studies evidenced that the bimetallic mole-
cule possessed the desired relatively lower symmetry respect to
a tpcorrCo, suggesting an improved catalytic performance for the
former system. Several parameters were taken into consideration
to identify the better performing hybrid catalyst, as pyrolysis tem-
perature and % loading of the binary catalyst on the carbon black.
Electrochemical studies together with ICP-MS and elemental anal-
ysis extracted 500 °C and 50% as the best temperature and precur-
sor amount of dpFccorrCo(PPh3) to disperse onto the supporting
carbon, respectively. In addition, XPS analysis gave information
about the composition of the active sites, found essentially Fe3+
and Co2+ species that are known to increase ORR catalytic activity
in other FeCo–N non-noble metal electrocatalysts. RRDE measure-
ments showed that the prepared hybrid catalyst reduces O2
through a direct 4-electron pathway, with less than 2.3% H2O2
yield, proving to be an interesting model for non-precious electro- Scheme 37. Au corrole complexes tested for solar cells development.
catalyst design for ORR.
Concluding this section, we find noteworthy to mention a very
recent paper by Major and coworkers, reporting a DFT investiga-
tion of the ORR mechanism in acidic media performed by several
octabromometallocorrole-based catalysts [MA(tpfcBr8)], where
M = Mn, Fe, Co, Ni and Cu [95]. Calculations showed that the coor-
dinated metal remarkably influences the LUMO orbital energy,
which has a metal-centred nature for Mn, Fe and Co complexes,
while it is quite concentrated on the macrocycle for the late tran-
sition metals Ni and Cu. This feature is reflected on a high oxo com-
plex stability for the first three metal complexes respect to the two
late transition metals, which accounts for the change in the poten-
tial determining step in the two cases. Since a good correlation is
obtained between the theoretical limiting potential with the
experimental onset potentials, the authors can conclude that these
intermediates are viable states along the reaction coordinate.
Eventually, the volcano-like plot obtained by plotting the experi-
mentally observed onset potentials as a function of the computed Scheme 38. tfpcorrGa-BODIPY heterodyad exploited in bulk heterojunction solar
O2 adsorption free energies, gives a negative binding free energy cells.
for the Co complex, which results the best catalyst of the investi-
gated set for the four-electron reduction of O2 directly to H2O.
tation of the corrole ring to respect the TiO2 surface, it also reduces
3.5. Solar cell applications
the electron withdrawing effect of the carboxy group, both factors
facilitating the electron injection from gold corrole to the semicon-
Despite their excellent photophysical properties, corroles have
ductor conduction band.
been seldom applied as chromophores in solar cells. After a semi-
More recently a tfpcorrGa-BODIPY heterodyad (Scheme 38) has
nal paper of Gross and coworkers on the exploitation of tpfcorrSO3-
been exploited as donor agent in a different design of solar cells,
Ga(py) in DSSC, with an overall efficiency of 1.9%, [96] the
the bulk heterojunction solar cells [99]. In these devices small
attention has been then devoted to the studies on corroles func-
molecules, such as corrole-BODIPY dyads, can efficiently substitute
tionalized with carboxy groups, used as grafting agent for
the polymers usually exploited, because they can offer a better
chemisorption onto TiO2 surfaces. Different 3-carboxy substituted
design, tunability of properties and so on. The conjugation of tpf-
corroles, both as free base or copper complex, were demonstrated
corrGa with BODIPY units offers the possibility to have chro-
to be scarcely efficient as photosensitizers in DSSC, by both exper-
mophores with high absorptions in a large section of the visible
imental and theoretical studies, probably because of a non favour-
region, high hole carrier mobility and synthetic flexibility. In the
able alignment of the energy levels of corrole and semiconductor
developed device, with the right choice of a suitable acceptor, it
for the electron photo-injection [97]. From this point of view, Bud-
has been possible to reach an efficiency of 6.60%, finally demon-
vig and coworkers demonstrated the possibility to solve this draw-
strating promising performances of corroles in solar cell applica-
back by tuning the properties of P corrole complexes by peripheral
tions, paving the way for their potential applications in these
substitution, although the efficiency obtained was almost similar
devices.
to that previously obtained by Gross [98]. Ghosh’s group more
recently has investigated the possible application of gold com-
plexes of meso-carboxyphenyl substituted corroles (Scheme 37), 3.6. Catalysis
obtaining the best efficiency with the corrole having the carboxy
group in the meta-phenyl position [16]. Iron (III)corrole complexes [100] [ttcorr-Fe(OEt2)2 and tpfcorr-
This result was probably due to both steric and electronic Fe(OEt2)2] have been used to chemoselectively catalyse the oxida-
effects: while the meta substitution led to an almost parallel orien- tion of sulfides to sulfoxides: these species are in fact valuable
Scheme 39. Proposed mechanism for the iron corroles catalyzed oxidation of sulfides to sulfoxides.
Scheme 40. (a) Oxygen rebound reaction for ttppcorrFeIV(OH), (b) rebound mechanism (top) and charge separation (bottom) in the transition state of the rebound reaction.
Scheme 41. Reaction of ttppcorrMnV(O) with 2,4-DTBP.
intermediates in the synthesis of natural products and biologically excellent chemoselectivity, high reactivity and improved stability
active molecules to be used in medicine and pharmaceutics. The of the catalyst, probably due to a slow and steady-state formation
use of several catalysts (polyoxometalates, flavins and metal of PhIO from the iodobenzene diacetate.
complexes, etc), in combination with H2O2, can induce the The authors, by means of UV-vis and Hammett correlation stud-
over-oxidation of sulfides to sulfones, while the use of corrole com- ies, suggested for this reaction the formation of putative corrole-
plexes, using iodobenzene diacetate, PhI(OAc2)2, as the sacrificial iron(V)-oxo intermediate as the active oxidant, relaxing to a radical
oxidant, in presence of a small amount of water, allows an cation compound through internal electron transfer (ET) from the
Scheme 42. Plausible mechanisms for HAT by MnV(O) complex.
macrocycle to the metal ion or undergoing rapid comproportiona-

tion reaction with the residual iron (III) corrole to give the stable
iron (IV) l-oxo dimer (Scheme 39).
Among the iron complexes, high valent metal hydroxide inter-
mediates have been studied [101]; they are involved in many nat-
urally occurring processes, including O2 activation and production,
but only rare examples of mononuclear MIV(OH) have been
reported for the first row transition metals, due to their tendency
to give hydroxy- or l-oxo dimers and to their redox instability.
Goldberg and his group reported the synthesis of FeIV(OH) [102]
using the large steric encumbrance of the ttppcorr ligand, previ-
ously reported, to prevent the l-oxo dimer formation. The iron
complex obtained was used to model the oxygen rebound reaction
for alkane hydroxylation, examining a series of trityl derivatives
(p-XC6H4)3C (X = OMe, tBu, Ph, Cl) varying the electron-donating Scheme 43. Manganese-Oxygen intermediates formed in the O2-activation and
properties of the para-X substituent (Scheme 40). OAO bond formation.
The authors, by Hammett and Marcus plots, determined the
rebound reaction to proceed via a concerted pathway (diagonal
path, Scheme 40b) with a transition state likely closer to the struc- a transient phenoxyl radical and in the formation of the MnIV(OH)
ture shown in Scheme 40, thus allowing further studies on the fac- complex, but no evidence of the hydroxide complex formation has
tor favouring and controlling the process. been found. This led to hypothesize two possible mechanism
The use of the above mentioned bulky corrole ligand also (Scheme 42): in the first one, the MnIV(OH) complex is a faster H
allowed Goldberg’s group to isolate a MnIV(OH) complex [103], abstractor than the starting Mn(V) complex, while in the second
as confirmed for the first time by X-ray diffraction. They also iso- one MnIV(OH) species disproportionates to give Mn(V) and Mn
lated, and structurally characterized, the MnV(O)ttppcorr and the (III), with Mn(V) being the sole oxidant in the system.
corresponding MnIII(H2O) complex, thus obtaining a series of man- Based on this finding, they tested the reactivity of the Mn(IV)
ganese complexes [MnV(O), MnIV(OH), MnIII(H2O)], with three dif- hydroxide complex: the reaction with 2,4-DTBP in benzene,
ferent oxidation and protonation states in an identical resulted in the rapid conversion on the starting corrole complex
porphyrinoid ligand environment, representing a unique opportu- to the Mn(III) aqueous compound, together with the formation of
nity to study HAT processes. The studies were initially done with the bis(phenol) dimer in good yield, consistent with a single HAT
9,10-dihydroanthracene, as the common substrate for the evalua- to MnIV(OH) to give MnIII(H2O). The rate of the process was mea-
tion of high-valent metal-oxo complexes in HAT reactions, but sured leading to a second-order rate constant, and the comparison
MnV(O) reacted very slowly; on the other hand, it revealed to be with the rate constant for the deuterated derivative of 2,4-DTBP,
able of abstracting H atoms from aryl OAH bonds with relative together with the other acquired data and what reported in litera-
ease. In presence of 2,4-DTBP, MnV(O) converted to the MnIII- ture for manganese complexes, led to the conclusion that HAT was
aquo complex leading to the formation of the phenol radical cou- the rate-determining step. In this case the HAT reaction with 2,4-
pling product in excellent yields (Scheme 41). DTBP proceeded much faster than the higher-valent MnV(O) com-
The coupled dimer was the expected product resulting from plex. The absence of this latter compound in the reaction medium,
ArOAH bond cleavage, which should initially result, after HAT, in confirmed that no disproportionation took place during the
process, thus supporting for mechanism A (Scheme 42). The opment of different catalytic systems for the application in the
authors concluded that the higher oxidation state of corrole com- synthesis of cyclic carbonates. Among the others, several metal
plexes does not always lead to have a better oxidant: MnIV(OH) porphyrins have also been used [109], but the authors reported
resulted with the same series of phenol substrates to be a more the use of a corrole complex for this kind of application, obtaining,
powerful oxidant than MnV(O), but also than FeIV(O) complexes, under mild conditions, NIPU with good thermal stability and a
widely invoked to be potent oxidants. satisfying tensile strength (8 MPa) in particular using 1,2-
Mn(III) corroles instead, tpfcorrMn(III) and tpfcorrCNMn(III), ethanediamine with carbonated canola oil (Scheme 44). A reduc-
have been used by Nam and coworkers [104] in dioxygen activation in the reaction time represented an interest success of the
tion [105] and the OAO bond formation. In biomimetic studies corrole catalyst as compared to the previously reported systems.
iron-oxygen intermediates bearing both porphyrin and nonpor- As a matter of fact similar results were previously obtained by
phyrin ligands [106,107] have been extensively used as model Waser and Schöfberger [110] in the CO2 fixation with epoxides
compounds and their formation mechanism has been elucidated, under mild conditions: based on the recent progress in the use of
but also high-valent manganese-oxo intermediates have been con- cooperative metal complexes/quaternary ammonium salt catalyst
sidered as reactive species. systems [111], they compared the catalytic activity of several tpf-
The authors reported the formation of Mn(V)-oxo and Mn(IV) corr complexes (manganese, iron, cobalt, copper, antimony and
peroxo complexes, when both the Mn(III)corrole complexes were bismuth) with TBAB, as a cheap nucleophilic organic halide source,
exposed to O2, in presence of hydrogen atom donors and base for the reaction of epoxides with CO2. In particular, they identified
(Scheme 43) and depending on the amount of tetramethylammo- the Mn corrole to have superior catalytic performances and found
nium hydroxyde used, whose role was to lower the oxidation out the best conditions for the reaction with styrene oxide (Mn
potential of the Mn(III) complex, facilitating the binding of oxygen corrole 0.05% and TBAB 2%), leading to the higher conversion
and the formation of a Mn(IV)superoxo species. The reverse reac- (higher than 95%). In order to further explore the scope of the reac-
tion of the OAO bond formation, is the OAO bond cleavage reaction tion, they investigated the reactivity of their catalytic system using
upon addition of H+ to the Mn((IV)peroxo leading to the Mn(V)-oxo other simple epoxides (Table 1)
corrole. Thus they demonstrated the same corrole complex can be Based on the data already reported in literature [12,112] they
useful both in O2-activation and OAO bond formation reaction. proposed the mechanism reported in Fig. 14, supporting their
The same tpfcorrMn(III) has been explored by Malik and Kaur hypothesis by DFT calculations of the three main intermediates
[108] for the green synthesis of PU: if the polyols necessary for A-C of the reaction and investigating the UV-vis spectral changes
the preparation of PU can be in fact easily obtained from cheap that occur to the catalyst during the process.
and non toxic vegetable oils, the use of toxic isocyanates still rep- The authors attributed the dramatic changes observed during
resents an issue to be solved. For this reason the authors used the the reaction in the absorption spectra to the axial binding of the
corrole complex for the introduction of cyclic carbonate moieties ring-opened epoxide, through the oxygen atom, and to the forma-
into epoxidized canola oil, to obtain NIPU by curing with various tion of the intermediate B after the CO2 insertion/fixation. It is
diamines. After the discovery that CO2 can be applied in polymer worth mentioning that they reported the recycling of Mn-corrole
synthesis to produce alternative copolymers, it has been used in to be possible and that their Lewis-acidic manganese corrole com-
the preparation of biomaterial-based polymers: it is abundant, lar- plex can be reusable for other transformations.
gely available, and present low toxicity. Unfortunately, the low The same catalytic reaction was investigated by Li and Cao
reactivity of CO2 limited its utilization, thus prompting the devel- [113]. In particular, through DFT calculations on different metal
Scheme 44. Synthesis of NIPU using a corrole catalyst. Reprinted with permission from Ref. [104]. Copyright 2018 Wiley.
Table 1
The catalytic scope of CO2 fixation by tpfcorrMn.
Ra T [°C] t [h] Conv.b [%] Yieldc [%] TONd TOFd [h1]

Ph 60 8 >95 94 1880 235
Ph 25 8 25 24 480 60
4-Cl-C6H4 60 8 >98 96 1920 240
4-F-C6H4 60 8 >98 98 1960 245
PhOCH2 60 8 >95 94 1880 235
PhCHOCH2 60 8 71 70 1400 175
ClCH2 60 8 89 88 1760 220
Vinyl 60 8 >98 93 1860 232
But-3-enyl 60 8 >98 98 1960 245
But-3-enyl 25 20 >98 98 1960 98
Me 25 8 57 55 1100 137
Me 25 20 >95 88 1760 88
a
4 mmol scale (neat).
b
Judged by 1NMR of reaction mixture.
c
Isolated yield after filtration over a short plug of silica.
d
TON = turnover number; TOF = turnover frequency.
Fig. 14. Proposed synergistic catalysis mode for Mn corrole. Adapted with permission from Ref. [112]. Copyright 2017 Wiley.
porphyrins, they predicted the preparation of cyclic carbonates by reducing the free energy barrier for the ring closure in the coupling
CO2 fixation to epoxides using PPNX (X = Cl, Br, I) as cocatalyst. The reaction (Fig. 15).
same calculations were done for an Al-corrole complex, leading to A theoretical investigation of the electronic and catalytic prop-
the conclusion that the metal corrole complexes exhibit similar erties for the complexes of tpcorr with some post-transition met-
activity for CO2 coupling to the epoxide in comparison with the als, including Al, Ga, Ge, Si and As, was done by Mohajeri and
metalloporphyrin complexes. In the case of corrole, PPNI resulted Hassani [114].
to be the most promising cocatalyst, increasing the free energy bar- In details, they investigated the mechanism of catalytic
rier for the ring-opening step to some extent, while remarkably oxidation of carbon monoxide for the above mentioned corrole
cation coordinated porphyrinoids, as for example vitamin B12,

and by electrochemical reductive catalysis using metallocorroles
as functional catalysts. For this reason, the mentioned research
group analysed the suitability of three meso-substituted metallo-
corroles for the electrocatalytic dechlorination and the relationship
between their electronic structures and the process efficiency.
Spectroscopic, electrochemical and spectroelectrochemical
measurements have been used to determine the mechanism of
the reaction leading to chlorobenzene as the final reaction product,
by [corrole Co(I)]2: the doubly reduced species of tpcorr resulted
the strongest anionic nucleophile, thus having the higher catalytic
efficiency. According to these studies, corrole substituents strongly
affect the catalytic reactivity of the macrocycle, which can be
enhanced by finely tuning of their electronic structure.
Liu and his group [117] instead reported their recent results in
the use of cobalt corroles for catalytic oxidation of alkene. In this
Fig. 15. Predicted relative free energy profile and electronic energies for the Al- case four diverse cobalt(III) corroles bearing different numbers of
corrole catalysed cycloaddition reaction in presence of PPNCl. Reprinted with pentafluorophenyl and phenyl groups have been studied (F15-
permission from Ref. [114]. Copyright 2018 American Chemical Society.
corrCo, tpcorrCo, F10corrCo and F5corrCo): two of them (F10corrCo
and F5corrCo) are new compounds. Being the redox properties of
cobalt corroles influenced by the presence of electron-donating
complexes, and stated that, with the only exception of As com- or electron-withdrawing groups, they studied the four compounds,
plexes, where the metal ion lies out of the macrocycle plane, for with a triphenylphosphine axially bounded, in different solvents
the other metal complexes the hybridization between M and (DMF, DMAc, DCM and CH3CN) since, as reported for chromium-
molecular oxygen leads to the activation of O2. For Si and Ge com- oxo corroles and molybdenum corroles, the solvent exerts an effect
plexes, the formation of a stable carbonate-like intermediate does in catalytic oxidation reactions (Scheme 45) [118].
not allow the CO oxidation reaction to further proceed, while Al The best choice, based on the yield of benzaldehyde formed in
and Ga complexes facilitate the activation of oxygen and subse- the reaction with PhI(OAc)2 as the oxidant, resulted to be acetoni-
quently promote the oxidation of CO. Their calculated energy bar- trile, so they used it for the optimization of the other reaction con-
riers (0.65 and 0.68 eV respectively for Al and Ga complexes, ditions. Different oxidants in CH3CN were then analysed, obtaining
respectively) are comparable with those previously obtained for the best results with PhI(OAc)2 and tert-butyl hydroperoxide, when
other metal-carbon surfaces, suggesting that they can be used as benzaldehyde was found to be the main product of the reaction.
potential high-performance catalysts for CO oxidation. This allowed them to do some mechanistic considerations and
Among the metal complexes, cobalt corroles have been largely define a plausible mechanism (Scheme 46) for the catalytic oxida-
applied as catalysts: their main application is in ORR, HER and tion of styrene by cobalt corroles, involving a Co(V)-oxo species as
WOR, but other kind of reactions can be performed by Co(III) and the reactive compound.
Co(IV) corrolates [115]. Goswami et al., due to the importance of nitrogen-containing
Zhu et al. recently reported [116] the use of a series of Co(III)- ring compounds for example in pharmaceutical, studied the effect
corroles [tpcorrCoIIIPPh3, 5,10,15-tris(4-fluorophenyl)corrCoIIIPPh3 of cobalt(II) porphyrin catalysts [119] in the intramolecular CAH
and 5,10,15-tris(4-carboxymethylphenyl)corrCoIIIPPh3] as electro- amination reactions by organic azides as nitrene precursors, to
catalyst for the dechlorination of lindane, the c-type hexachlorocy- form N-heterocyclic compounds and based their hypothesis on
clohexane (HCH), under mild electron reductive conditions. Such a the reaction mechanism (Scheme 47), they suggested that a more
compound, used for a long time as agriculture insecticide and in electron rich scaffold [120], retaining the same square-planar
pharmaceutical treatment for lice and scabies, is one of the most geometry, could be beneficial for activating aliphatic azides.
known persistent organic pollutants, whose presence can seriously The azide activation step in fact occurs with the oxidation of
damage human health and ecosystems even at low concentration, cobalt(II) to cobalt(III), thus leading to the nitrene radical interme-
since it tends to bioaccumulate in lipid-rich tissue, causing damage diate formation; for this reason, the presence of a ligand imposing
to the nervous system. Precious and expensive metal complexes a higher electron density at the cobalt center can lead to make fas-
are generally used to protect humans and environment by partial ter the catalytic reaction, decreasing the barrier of the rate-limiting
or full dechlorination of lindane, but the same dechlorination can N2-dissociation step: three corroles with electronically different
be achieved, under vigorous conditions, using transition metal- substituents (bis-dibromophenyl-phenyl corrole, tpcorr,
Scheme 45. Oxidation of styrene catalysed by corrCo(III).

Scheme 46. Proposed mechanism for the oxidation of alkenes by cobalt corroles.
dimesityl-trimetoxyphenylcorrole) have been used to study the The authors synthesized an unusual heterobimetallic com-
feasibility of the macrocycle as a ligand in cobalt catalysed pound, with a covalent, weakly polar SnACo bond. Such a com-
nitrene-transfer reaction. pound can undergo SnACo homolysis under thermal and
Cyclic voltammetry (CV) was used to study the first reduction photochemical conditions, leading to the first observation of an
waves and the corresponding re-oxidation waves of Co-corrolates active and four-coordinated stannyl radical. This kind of radical is
that showed the expected redox behaviour compared to the related usually rare and unstable due to the reluctance of the Sn(III) centre
compounds (Scheme 48). to accept a fourth ligand: in the case of corrole, the use of a rigid
EPR spectroscopic and UV-vis spectroelectrochemical measure- and non innocent ligand forced the coordination around the tin
ments were carried out to confirm the electrochemical-chemical- centre and contributed to its stability. The resulting catalyst, taking
electrochemical-chemical (ECEC) mechanism: by a chemical advantage of the unusual reactivity of the Sn centre, has been
reductant all the corrole complexes have been then reduced to give applied and studied in the oligomerization of aryl alkynes to give
the cobalt(II) metalloradicals, as confirmed by EPR. Their activity both insertion products [(tpfcorr)SnA(CH)C(Ar)]nACo(TAP) (n = 1,
and selectivity have been then tested in the direct ring-closing 2 or 3) and 1,3,5-triarylbenzenes.
reaction of (4-azidobutyl)benzene to give the N-heterocyclic
pyrrolidine product (Scheme 49).
The authors reported that when cobalt complexes of porphyrins 4. Biological and medical applications
are used for this reaction, the Boc protected pyrrolidine product is
selectively obtained, while the increased electron density of cor- 4.1. Anticancer applications
role, reducing the barrier of the rate-limiting azide-activation step,
can increase the rate of the ring-closing CAH amination reaction The exploitation of corrole derivatives for cancer treatment has
even if the selectivity was somewhat compromised by the forma- been recently reviewed [71]. Triarylcorroles have shown promising
tion of the linear N-Boc-protected amine. activity as photosensitizers in PDT, due to their peculiar optical
Besides corrole complexes, also heterobimetallic compounds properties. In most studies, the corrole ring has been functional-
have been studied: as a matter of fact, their unconventional bond- ized with charged substituents, while, more recently, tpfcorr has
ing properties can enable them to act as catalysts. Wang et al. [121] been modified with hydroxyl groups to enhance its availability in
focused on a transition metal (TM)-tin complex, namely a (tpfcorr) biological media (Scheme 51) [122]. The binding of DNA and the
Sn-Co(TAP), since the introduction of TM-tin bond generally leads activity as photosensitizers towards tumor cells of this macrocycle
to an increase in the catalysis rate, with the tin-containing group and the corresponding Ga complex were investigated.
usually acting as a spectator, which modifies the TM centre by UV-visible spectroscopy showed hypochromic change and red
electronic effects, rather than directly participating to the process shifts of Soret bands upon DNA interaction, suggesting external
(Scheme 50). binding for both free base and Ga complex, a hypothesis confirmed
Scheme 47. Proposed mechanism for catalytic ring-closing CAH amination of an aliphatic azide.
upon light irradiation, and the mechanism of the photocleavage

was attributed to the production of singlet oxygen. Fluorescence
imaging revealed the localization of the corrole in the cell nuclei,
and the macrocycles showed phototoxicity in vitro against
different cellular lines, showing promising properties for PDT
application.
The same group investigated the DNA binding activity of
5,15-bpfp-10cpcorrGa and 5,15-bcp-10-pfpcorrGa derivatives
(Scheme 52) [123].
The DNA binding interaction of these complexes was evaluated
by fluorescence spectroscopy, observing the emission quenching of
Scheme 48. Representation of the species present during the reduction and re-
the Ga corroles in the presence of CT-DNA, due to the formation of
oxidation events in the CV scan.
a non-fluorescent corrGa-DNA complex. The absorption spectra
gave indication of a groove binding mode, as confirmed by the vis-
by the fluorescence quenching and the reduction of the solution cosity measurements with the 5,15-bpfp-10cpcorrGa, which
viscosity observed in the same conditions. The Ga complex showed showed a higher affinity, confirmed also by docking calculations,
higher activity in DNA cleavage than the corresponding free base with binding sites located in the major groove of DNA helix.
Scheme 49. Ring-closing reaction of (4-azidobutyl)benzene.

Scheme 50. Heterobimetallic Co-porphyrin-Sn-corrole catalyst.
Scheme 52. Molecular structures of Ga corroles tested in DNA binding studies.
demonstrated by 5,15-bpfp-10cpcorrGa was also correlated to a

Scheme 51. Molecular structure of hydroxyl-modified Ga pentafluorocorrole better rate of singlet oxygen production. Both corroles were accu-
photosensitizer. mulated in the mitochondria of tested cells, which is an important
detail for their potential efficiency as photosensitizers to induce
cell apoptosis.
Thanks to the higher affinity, 5,15-bpfp-10cpcorrGa showed The same group has also studied the behaviour of tEtcorrGa(py)
also a higher photocleavage activity of DNA than 5,15-bcp-10- and tEtcorrMn complexes (Schemes 51 and 53) as photosensitizers
pfpcorrGa. The photocleavage mechanism was demonstrated to in photodynamic therapy [124]. The advantage of the tEtcorr has
be induced by singlet oxygen production and the higher activity been attributed to its better ability to cross the cellular membrane
essential for the in vitro phototoxicity against SiHa cells

(Scheme 54) [126].
While the free base did not show cytotoxicity in vitro, although
it was the best producer of singlet oxygen, the Ga complex showed
low toxicity under the dark, which was enhanced by six times
upon light exposure. Fluorescence imaging showed the Ga
corrole-coumarin dyad localized both in the cytoplasm and in the
nucleus of SiHa cells, and the PDT treatment led to cell apoptosis,
evidence by DNA damage.
The potential application of tin corrole complex in PDT was
recently studied [127]. UV-visible spectroscopy, Circular Dichroism
spectra, solution viscosity changes and Molecular docking studies
supported an external binding mode of Sn corrole with CT-DNA.
When incubated with DNA Sn corrole showed an efficient cleavage
Scheme 53. Molecular structures of Ga and Mn tEtcorr photosensitizers.
activity under illumination, with a mechanism correlated by the
production of superoxide anion radical, as indicated by the
exploitation of different ROS scavengers and EPR studies. Singlet
than the previously studied meso-arylsubstituted corroles, thanks
oxygen production was instead negligible. When incubated with
to the planarity of the corresponding complexes.
human lung carcinoma cells, Sn corrole showed high cytotoxicity
The two complexes were tested as photosensitizers with differ-
both in the dark and upon light exposure, with no significant dif-
ent types of human lung carcinoma cell lines. Both complexes
ference among dark and light conditions, suggesting that the toxi-
showed low cytotoxicity in the dark, but while Mn complex
city was not dependent on light irradiation. The cells death seems
showed no variation upon light exposure, the tEtcorrGa showed a
not be related to apoptosis route.
sharp increase of phototoxicity in these conditions. For this reason
the following studies were carried out using the Ga derivative. The
cellular uptake of tEtcorrGa was revealed by the red fluorescence 4.2. Photodynamic inactivation
observed in cells, without the need of transmembrane carriers,
needed for example by the analogous water soluble tpfcorrSO3Ga The potential application of corrole derivatives in the PDI of
(Fig. 16). The phototoxicity of tEtcorrGa was demonstrated to be bacteria and fungi has been recently explored. Cardote et al. stud-
due to the production of ROS, which were responsible of the cell ied the antibacterial activity of Ga complexes of cationic corroles
apoptosis. (Scheme 55) against bioluminescent Gram-negative bacteria
The efficiency of tEtcorrGa as PDT agent was tested in vivo in [128]. The PDI activity of Ga corroles was compared with that of
human tumour xenografts in murine models, showing high poten- the previously studied tpyMePI; the kinetic of the PDI was similar
tials with higher activity than porphyrins. at higher concentration of photosensitizers, while ttfsppycorrGa
The conjugation of the same tEtcorrGa with a tumour- (py) was able to obtain the complete photoinactivation of bacteria
associated antigen (CT83) has been studied, with the aim to in a shorter time than the corresponding porphyrin.
improve the selective delivery of photosensitizers to target tumour A first study interesting the potential application of tpyMePI
cells [125]. The developed tEtcorrGa-antigen conjugate showed a and the topycorrP(OH)2 (Scheme 56) for the therapy of onychomy-
greater phototoxicity than the corresponding single tEtcorrGa cosis has been recently reported [129]. The study was dedicated to
towards human tumour cell lines, demonstrating promising poten- investigate the potential application of bidimensional lumines-
tial application of this route in PDT. cence scanning of both photosensitizers and singlet oxygen to eval-
Corrole-coumarin dyads have been recently synthesized and uate the PDI of fungi onto target surfaces. This is the first step for
tested as photosensitizers, showing again that Ga coordination is the potential application of PDI as onychomycosis treatment.
Fig. 16. Comparison of the cellular uptakes of tEtcorrGa and tpfcorrSO3Ga. Reprinted with permission from Ref. [125]. Copyright 2017 Royal Society of Chemistry.
with the neurotoxin 6-hydroxydopamine, they discovered that Fe

corrole was able not only to mitigate the oxidative stress induced
by the neurotoxin, but also to prevent the cell death when it was
added after the neurotoxin treatment. This result suggested that
the action of Fe corrole is not limited to an antioxidant effect,
but it can also perform a recovering effect [76b]. To study in
better detail this rescuing action, the same group investigated
the Fe corrole interaction on the apoptotic pathway on SN4741
cells treated with 6-hydroxydopamine [132]. The cell line was cho-
sen as in vitro model of the neuronal damages involved in the
Parkinson pathology. Using the luminescent analogous Al corrole
to study the cellular uptake, they found that Al corrole is dispersed
in the cytosol and in diverse organelles, but it is also accumulated
in the mitochondria. The neuroprotective action of tpfcorrSO3Fe
was tested by adding 6-hydroxydopamine to SN4741 cells pre-
treated with the complex and comparing the results with native
Scheme 54. Molecular structure of Ga corrole-coumarin dyad tested against SiHa
cells. In the presence of tpfcorrSO3Fe the cell survival was up to
cells.
80%, to respect the 5% observed with the control cells, demonstrat-
ing the efficient neuroprotective action of tpfcorrSO3Fe.
However tpfcorrSO3Fe was also able to induce the cell survival
Photosensitizers were deposited onto filter paper and then placed even when administrated after the 6-hydroxydopamine dosing,
onto Agar Petri dishes; a spore suspension of fungi was then pipet- also when the corrole was added two hours later than the addition
ted in the Petri dishes, which were kept in the dark. Both photosen- of 6-hydroxydopamine. This feature led to investigate the influ-
sitizers fluorescence and singlet oxygen phosphorescence were ence of tpfcorrSO3Fe on the levels of anti- and pro-apoptotic pro-
registered over 24 days, demonstrating that the technique can be teins. It was found that the administration of tpfcorrSO3Fe to the
useful for the optimization of PDI conditions. The photosensitizers SN4741 cells before the 6-hydroxydopamine increased the concen-
showed a similar behavior, but with a different action pathway. P tration of the antiapoptotic protein Bcl-2. More in detail, the study
corrole was in fact able to diffuse from the filter paper to the agar, showed that the tpfcorrSO3Fe action is initially the ROS scavenging,
a diffusion not showed by the porphyrin. but the corrole is also involved in different mechanisms that result
in the observed neuro-rescue effect, such as the increase of the
4.3. ROS decomposition antiapoptotic protein Bcl-2 level. The different processes are
schematically reported in Fig. 17.
Gross and coworkers have reported the excellent catalytic prop-
erties showed by the Iron complex of tpfcorrSO3 for the decompo-
sition reaction of ROS [130], testing the potential application of this 4.4. Chemical sensors
corrole for the prevention of the damages induced by cellular
oxidative stress both in vitro and in vivo in animal models [131]. The peculiar coordination chemistry of corrole makes the metal
However, in the case of neuroblastoma cell lines SH-SY5Y treated complexes of this macrocycle of interest as receptors in chemical
Scheme 55. Molecular structures of Ga cationic corrolates investigated by Cardote et al. [128]
Scheme 56. Molecular structure of topycorrP(OH)2 investigated as PDI agent for

onychomycosis treatment.
Fig. 18. SEM image of Co corrole functionalized polyacrolein microspheres

deposited from ethanol suspension. Reprinted from Ref. [39]. Copyright 2017 Wiley.
sensor development, because the metal axial binding is one of the

most important interaction among sensing material and target
analytes. The corrole application in chemical sensors has been
recently reviewed [70], and we report here the most recent reports
in the field.
4.4.1. Oxygen sensor

Oxygen sensing has been one of the widely studied sensor
applications, because the molecular oxygen detection is important
in several fields. Pd and Pt complexes of porphyrins have been
exploited in these devices, with the sensing mechanism based on
the macrocycle phosphorescence quenching [70]. Gold corroles
show a Near-IR phosphorescence emission and for this reason they
can be of interest to develop optical oxygen sensors in biological
samples. To respect Pd and Pt porphyrins, in fact, Au corroles show
a red shifted emission, with the correct lifetime, which make them
more suitable for the analysis of biological samples. Nocera and
coworkers have reported the photophysical characterization of
the b-substituted 5,15-bpfp-10cpcorrAu derivatives reported in
Scheme 57, and the corresponding oxygen sensing behaviour
[133]. The room temperature phosphorescence emission of Au cor-
roles was quenched by air, showing that this corrole is sensitive to
molecular oxygen in a range interesting for biological applications.
Concerning these potential advantages, Au corroles have a single
Fig. 17. Neurorescue action of tpfcorrSO3Fe. Reprinted with permission from Ref.
drawback to respect the corresponding metalloporphyrin, which
[12]. Copyright 2016 Elsevier.
is related to the relatively less intense phosphorescence quantum
Scheme 57. Molecular structures of 5,15-bpfp-10cpcorrAu and the brominated derivatives reported by Nocera and coworkers as oxygen sensitive materials [133].
Fig. 19. Dynamic responses of functionalized microspheres with acrolein/corrole ratio of 250:1 (PACorr 250:1), pure polyacrolein (PA) and corrole towards A) hexane and B)
ethanol. Reprinted with permission from Ref. [39]. Copyright 2017 Wiley.
Fig. 20. hiPSCs samples analysed by sensor array. Reprinted with permission from Ref. [134], which is an open access article distributed under the Creative Commons
Attribution License (CC BY), MDPI.
yield, which is in the range of 0.3% for the Au corroles, significantly poly-acrolein microsphere) components. Furthermore, the
lower than that of Pt porphyrins. response dynamics were strongly influenced, depending on the
polar nature of the VOC (Fig. 19). All these features make the func-
4.4.2. Sensor arrays (gas phase) tionalized microspheres particularly promising to develop QCM
The 3-acrolein substituted Cobalt corrole has been co- sensors.
polymerized with acrolein to give functionalized polyacrolein Copper corrole based nanogravimetric sensors were integrated
microspheres (PACorr). The functionalized spherical particles had in sensor arrays and the potential applications of these devices
an average diameter of 800 nm (Fig. 18) and were exploited as for the characterization of stem cell differentiation [134,135] and
sensing material of QCM [39]. Two different kinds of functionalized for the early diagnosis of pathologies has been investigated
microspheres were investigated, by changing the corrole/acrolein [136]. These arrays are based on low selective sensors and the
ratio. exploitation of porphyrinoids together the working mechanism of
The microspheres were deposited onto the surfaces of QCM by these devices has been previously reviewed [70,137]. Corrole
drop coating technique from ethanol suspensions. When exposed derivatives can contribute to improve the performances of these
to model VOC, the functionalized microspheres showed higher devices because their behaviour is different from that of the anal-
sensitivities to respect the individual (Co corrole and pristine ogous porphyrins, enlarging the sensitivity and selectivity range of
4.4.3. Sensor arrays (liquid phase)

Following the array approach also in the liquid phase, a phos-
phorus corrole has been exploited in an optical sensor array for
the detection of water sample pollutants [139]. The optical sensing
platform was realized by using cheap commercial devices, such as
a LED as light source and a web camera as a detector (Fig. 13). The
sensing mechanism was based on the fluorescence quenching
induce by the interaction with the target analytes. P corrole was
in particular sensitive to nitrite ion (Fig. 21), with the array show-
ing promising performances for the monitoring of pollutants in
water samples.
4.4.4. Ion selective electrodes

A different exploitation of a Co corrole has been recently
reported, where the complex has not been used as receptor, but,
together a corresponding Co porphyrin, it has been used to
improve the characteristics of potentiometric all-solid-state ion
selective electrodes [140]. Problems of these devices are related
to the stability of the potential readings, together a lack of repro-
ducibility of the potentials in different batch of nominally identical
sensors, which requires their calibration before the measurements.
It has been reported in the literature that the exploitation of a Co
Fig. 21. Optical sensor array set-up exploited for water pollutant detection.
Adapted from Ref. [139], which is an open access article distributed under the (III)/Co(II) redox couple in the polymeric membrane can improve
Creative Commons Attribution License (CC BY), MDPI. the potential stability of the sensors [141]. This effect has been
related to the action of the redox couple as a redox buffer that sta-
bilizes the sensor potential. However the ion flux generated by the
the sensor array. In the last few years a challenging application of redox conversion reduced the detection limits of the resulting sen-
these devices has been related to the analysis of the so called vola- sors. To avoid this effect, a mixture of tbupporCo(II) and tbup-
tilome, i.e. the volatile fraction of metabolites, as source of informa- corrCo(III)(PPh3) has been proposed; these complexes are not a
tion for the characterization, both in vitro and in vivo, of biological redox pair, because they cannot be interconverted and conse-
samples. quently they do not originate ion fluxes, but, on the other hand,
In a first report, a nanogravimetric sensor array including cor- they can stabilize the potential, because they have independent
role derivatives has been exploited to follow the different steps redox processes, producing a stable mixed potential.
of the in vitro differentiation of pluripotent stem cells by the anal- To test the efficiency of the system, the mixture of Co porphyri-
ysis of their volatile metabolites. Human induced pluripotent stem noids was used together multiwalled carbon nanotubes in an ion
cells have been proposed for the study of different pathologies and selective potentiometric sensor constituted by a potassium iono-
also as a potential alternative route in transplants, to avoid phore dissolved in poly-vinyl chloride membrane deposited onto
immune responses. However the risk is to inoculate not fully dif- a glassy carbon electrode. The results obtained showed a beneficial
ferentiated cells, which can induce the formation of teratomas effect of the application of the porphyrinoid mixture, with a signif-
[138]. The sensor array was used to follow the cell reprogramming icant stabilization of the electrode potential, with also high repro-
of chorionic villus samples to hiPSCs and then during their differ- ducibility and an overall improvement of the sensor performances.
entiation process through the analysis of the volatile metabolites The promising results led to follow the same approach to
emitted in vitro (Fig. 20) [134]. develop disposable potentiometric sensors, using paper substrates,
The array was able to well discriminate the hiPSCs to respect with the structure reported in Fig. 22 [142]. The application of the
the other cells, showing also the capability to discriminate all the mixture of porphyrinoids resulted in the high reproducibility of the
different steps of cell differentiation. The result obtained was vali- sensors potentials for different batch of them. Furthermore, these
dated also by GC-MS analysis, illustrating promising perspectives potentials showed only slight changes when measured for different
of a non-invasive method for the identification of residual, non- days, but the reproducibility of them was maintained. These
differentiated cells in sample of differentiated cells. In a subse- results are particularly promising for the application of these sen-
quent work, the same approach has been exploited to follow the sors in the real field.
cell differentiation in vivo, following the volatile emitted by mice
transplanted with hiPSCs or embryoid bodies derived from hiPSCs 4.5. Deposition of metallocorroles on surfaces
at 5 days and spontaneously differentiated cells at 27 day [135].
Also in this case, both the gas sensor array and GC-MS analysis The metallocorrole applications in fields such as sensors and
were able to identify the formation of malignant teratomas before catalysis make interesting to characterize the deposition of these
that the cancerous mass became visible. This result further sup- species onto solid surfaces, because the morphology of the thin
ports the potential application of sensor array for early diagnosis layers strongly influences the characteristic of the resulting device
of tumour after surgery. or catalyst. However, only sparse examples of these studies have
In a different study, the same sensor array was exploited to been reported in the literature.
analyse the volatile compounds emitted by mice infected with A water soluble phosphorus corrole has been deposited onto an
murine malaria [136]. The study aims to the possible detection of Au(1 1 1) surface by a spray coating deposition technique from a
malaria infection, following the hypothesis that the pathology methanol solution and the functionalized surface has been charac-
induces the emission of volatiles to attract mosquitoes, to spread terized by STM [35]. The corrole deposited in low amount formed a
the infection. The sensor array was able to discriminate among molecular film that covered the Au(1 1 1) surface, with the P cor-
infected and non-infected mice, showing to be promising for the roles oriented almost parallel to the surface. The coverage was
application in the real field. non homogeneous, with holes randomly present on the surface
Fig. 22. Structure of the tbupporCo(II)/tbupcorrCo(III)(PPh3) paper based potentiometric sensor. Adapted from Ref. [142]. Copyright 2018 Elsevier.
(Fig. 23). The depth of these holes was compatible with the lack of In a subsequent work, the deposition of the P corrole layer was
molecules in the layered film. investigated by STM in water, a situation that is closer to the thin
The morphology was different when the phosphorus corrole film deposition conditions [143]. The deposition of the P corrole
was deposited by drop coating method; in this case STM images onto Au(1 1 1) surface forms rows of molecules with a length of
showed the formation of corrole aggregates. When the P corrole ten of nanometers, oriented in the same direction (Fig. 24). The
was deposited together Reduced Graphene Oxide, a high mobility dimensions of the rods were compatible with P corroles flat ori-
of the gold surface atoms was observed at the crystal edges, with ented on the surface, which could be attributed to the formation
the formation of nanofingers induced by STM scans. of electrostatic interactions among the charged sulfonyl sub-
Fig. 23. STM images of: a) Au(1 1 1) surface (90 90 nm2); b) and c) pits formation after P corrole spray coating deposition onto the Au(1 1 1) surface [b) 100 100 nm2; c)
50 50 nm2]; d) depth profile of the surface. Reprinted with permission from Ref. [35]. Copyright 2017 Wiley.
with the reduction peak obtained by Cyclic voltammetry in solu-

tion, demonstrating that in the solid state P corrole retains its
own features, a result important for the application of these species
in devices.
The possible metalation of free base corrole deposited onto Ag
(1 1 1) surface with iron has been recently investigated [144].
The aim of the work was to exploit corrole to investigate the pos-
sibility to obtain a iron complex with an oxidation state higher
than that of the corresponding Fe(II) porphyrins or phthalocya-
nines. The metalation was carried out on both mono- and multilay-
ers of corrole deposited in Ultra High Vacuum and the metalation
was determined by XPS analysis. In the case of multilayer films
XPS suggested that the metalation was possible for both corrole
and porphyrin, and it interested the first external layers. Also in
the case of monolayer, the metalation occurred for both macrocy-
cle, in a degree ranging among 35–40%. NEXAFS spectra recording
Fe L-edges showed differences among oepFe and hedmcorrFe, but
STM analysis gave more information on the different oxidation
state of the iron complexes, because they showed different con-
trasts in the STM images (Fig. 25).
5. Conclusions
The coordination chemistry of corrole derivatives has witnessed

an impressive boost in the last two decades and this interest is con-
tinuously refurbished by novel reports, as confirmed by the
impressive number of articles published in the last two years and
reported in this review. While the non innocence as ligand of cor-
role seems to involve a larger number of metal complexes and it is
a useful platform to study these metal-ligand interactions, it is also
for interest for the exploitation of metallocorroles in different
fields, ranging for energy conversion to clinical applications. The
Fig. 24. STM image of the Au(1 1 1) surface into a P corrole solution
superb optical properties of corrole derivatives are a further reason
(1.4 105 mol/L) concentration and the corresponding depth profile. Reprinted
with permission from Ref. [143]. Copyright 2018 Wiley. of interest, for both theoretical and practical purposes. All these
possibilities are now supported by the great improvement of the
synthetic chemistry of corroles, with the related ‘‘periodic table”
stituents and the Na+ counterions. The high mobility of the struc- now competing for extension and versatility with that of the
tures did not allow the molecular resolution, indicating also weak parent porphyrins. Nevertheless, a great effort should be done to
interactions among corrole and gold surface. The increase of the P elucidate in detail the metallocorrole features and to fully explore
corrole concentration led to a higher coverage of the Gold surface, the potential applications of such a species. For this reason, corrole
with the formation of clusters of molecules, probably due to the can be considered both as an old member of the porphyrinoid family,
overlap of different molecular layers. When the solvent was left but also as a youngster macrocycle with a brilliant future ahead.
to evaporate after the measurements, the subsequent STM images
in air show the formation of P corrole aggregates, which covered Acknowledgment
only the 2% of the surface; this result confirmed the images previ-
ously obtained by drop coating technique. The characterization of The support by the University of Rome Tor Vergata, Italy,
the electronic properties of the corrole layers showed similarity SensAir project-E81I18000180005 is gratefully acknowledged.
Fig. 25. STM images STM images of (a, c) unmetalated and (b, d–f) metalated hedmcorr and oep deposited Ag(1 1 1) surfaces. Reprinted with permission from Ref. [144].
Copyright 2018 American Chemical Society.
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Metal Corrole

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Metal Corrole

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Coordination Chemistry Reviews 388 (2019) 360–405

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

Metal complexes of corrole

1.1.3. 4d transition metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363

Scheme 2. Si-complexes obtained from aryl- and alkylcorroles.

are stable and exhibit remarkable chemical and photophysical

reaction of a free-base corrole and Pt4(OAc)82HOAc in benzonitrile

Scheme 6. Synthetic procedure for the preparation of ruthenium corroles.

exhibit strong ligand-to-metal electronic communication. In this

Scheme 7. Synthesis of stable Pt(IV) corroles.

Fig. 5. X-ray crystal structure of 5,15-tmp-10omepcorrTaCl2. Reprinted with

The bromo-copper complexes have been demetalated, under

sulfonation has been very useful for the preparation of amphiphilic

Scheme 11. Preparation of different tFccorrFe complexes.

led to the desired corroles 3,17-bis-PE-tpcorrCu and 3,17-bis-PE-

Scheme 13. Synthesis of halogenated copper corrole complexes.

Scheme 14. Iodination reaction of (tpfcorr)Co.

Scheme 16. Synthesis of p-extended b,b0 -pyrrolo(1,2-a)pyrazino-fused corroles.

2.1.4. Gallium corroles 2.2. Electrochemistry

2.2.1. Co corroles The first reduction of tmcorrCo in CH2Cl2 occurred at a potential

Scheme 17. Acrolein-ttcorr Cu and Ga complexes.

Scheme 18. Di- and octa-PE substituted p-extended copper corroles.

Scheme 21. Structures of iron tFccorr with different axial ligands.

irradiation, the EPR of the solution were registered in the presence

3.1. Energy conversion reactions

3.2. Hydrogen evolution reaction

The production of hydrogen gas from electrocatalytic water

whose activities can be finely controlled by combining the electron

Scheme 27. Redox processes of [corrol2Fe(III)]Cl.

[82]. For this aim, they prepared carbon-based hybrid materials

Scheme 29. General mechanistic pathway for HER electrocatalysed by Co corroles.

[pyridine(-py), 4-cyanopyridine (Apy-CN), 4-N,N0 -

Interestingly, the carbon material used had a remarkable impact on

is broadly reported. The investigated molecule, reported in

Scheme 41. Reaction of ttppcorrMnV(O) with 2,4-DTBP.

Scheme 42. Plausible mechanisms for HAT by MnV(O) complex.

macrocycle to the metal ion or undergoing rapid comproportiona-

Ra T [°C] t [h] Conv.b [%] Yieldc [%] TONd TOFd [h1]

cation coordinated porphyrinoids, as for example vitamin B12,

Scheme 45. Oxidation of styrene catalysed by corrCo(III).

upon light irradiation, and the mechanism of the photocleavage

Scheme 49. Ring-closing reaction of (4-azidobutyl)benzene.

Scheme 50. Heterobimetallic Co-porphyrin-Sn-corrole catalyst.

Scheme 52. Molecular structures of Ga corroles tested in DNA binding studies.

demonstrated by 5,15-bpfp-10cpcorrGa was also correlated to a

essential for the in vitro phototoxicity against SiHa cells

with the neurotoxin 6-hydroxydopamine, they discovered that Fe

Scheme 56. Molecular structure of topycorrP(OH)2 investigated as PDI agent for

Fig. 18. SEM image of Co corrole functionalized polyacrolein microspheres

sensor development, because the metal axial binding is one of the

4.4.1. Oxygen sensor

4.4.3. Sensor arrays (liquid phase)

4.4.4. Ion selective electrodes

with the reduction peak obtained by Cyclic voltammetry in solu-

The coordination chemistry of corrole derivatives has witnessed

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Scheme 27. Redox processes of [corrol2Fe(III)]Cl.