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Recent Advances in Vat Dyes Chemistry for Organic Electronics

Jean-François Morina
Received 00th January 20xx,
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Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
This review presents an overview of the recent development in the area of vat dyes chemistry for the preparation of π-
conjugated molecules and polymers for organic electronics applications. Vat dyes are well-established molecules for textile
colouring and painting industry as they are inexpensive and highly stable. Their optical properties in the visible region are
attributed to their highly conjugated sp2 carbon network and the presence of functional groups, especially ketones that
allow the formation of “leuco” species. In this review, we will show how the presence of functional groups on these highly
conjugated scaffold can be used to modify their electronic and optical properties to make them useful building blocks for
semiconducting organic materials.

presence of conjugated ketones within the dye structure.

1. Introduction

Neutral organic dyes possessing a π-conjugated structure are

drawing considerable attention as potential building blocks for
the preparation of highly efficient semiconducting materials
for various organic electronics applications. One of the biggest
advantages of these dyes is their optical properties in the
visible range, making them attractive for solar cells, both
organic (OSCs) and dye-sensitized (DSSCs), and light-emitting
diodes (OLEDs) applications. In addition, their large carbon-
rich, rigid π-conjugated structure allows for excellent charge
transport properties that could be exploited in field-effect
transistors (OFETs) and battery applications. Other noteworthy
advantages are their very low cost when buy in bulk owing to
the few, inexpensive synthetic steps required to prepare them,
their high environmental, thermal and chemical stability, and
the possibility of performing chemical transformation to
change their properties owing to the presence of functional
groups such as ketones, halogens and amines.
Vat dyes are a particularly interesting class of building
blocks for low-cost electronics since they are produced in large
amount - thousands of metric tons per year – for textile
Fig. 1 Structures and names of the vat dyes recently used as building blocks for
colouring. By definition, a vat dye is a molecule that can be the preparation of π-conjugated organic semiconductors.
reduced using an inorganic salt like sodium dithionite, allowing
the dye to become water-soluble. After the textile is soaked in Recently, many researchers explored the chemistry of vat
the reduced dye solution, the vat dye gets re-oxidized to its dyes to eventually introduce them as the active component in
neutral, insoluble form, thus giving stable colouration to the organic electronics applications. In fact, most of the vat dyes
textile. This process requires an easily accessible reduced possess a large π-conjugated system that provides efficient
“leuco” form, which is most of the time allowed by the light absorption in the low energy region of the visible
spectrum, making them very interesting building blocks for the
preparation of light-harvesting semiconductors for OSCs.
a. Département de Chimie and Centre de Recherche sur les Matériaux Fonctionnels Moreover, small molecules and polymers based on vat dyes
(CERMA), Université Laval, 1045 Ave de la Médecine, Québec, QC, Canada G1V
0A6. packed very efficiently with maximum π overlap in the thin-
*Email - jean-francois.morin@chm.ulaval.ca film state, which is highly beneficial to the charge transport
properties. This is particularly critical for the development of

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(OFETs) whose efficiency strongly depends upon thin-film
morphology. Finally, vat dyes-based molecules can be made
highly emissive by simple derivatization, which makes them
interesting candidates for organic light-emitting diodes
(OLEDs) applications.
Because of the unique reactivity of vat dyes, reliable and
efficient methodologies need to be developed in order to
functionalize and introduce them as building blocks in π-
conjugated materials. However, this is not a trivial task as most
of the commercially available vat dyes are quite insoluble in
common organic solvents and contain a non-negligible amount
of impurities. In this review, we discuss the recent
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developments in synthetic strategies used to prepare vat dyes-
based π-conjugated materials for organic electronics. The vat
dyes covered in this review are shown in Figure 1. It is
noteworthy that other dyes like quinacridone, 1
2 3
perylenediimide and diketopyrrolopyrrole are very important
to the field of organic chemistry and organic electronics.
However, because they have been reviewed extensively in the
recent years and that they are not considered vat dyes per se,
we will not address them in this review. Likewise, indigo (vat
blue 1) and isoindigo, which are very useful dyes for organic
electronics, has not been reviewed here since several
exhaustive reviews have been published on that topic. 4,5
Anthanthrone
Anthanthrone (1, Fig. 1) has been synthesized for the first time
more than a century ago by Ludwig Kalb from the Chemical
Laboratory of the Royal Academy of Sciences in Munich. 6
Nowadays, anthanthrone derivatives are prepared
commercially from naphtholactam 10, which is hydrolyzed,
diazotized and dimerized (Fig. 2).7,8 Halogenation in 4 and 10
positions can be performed using molecular chlorine, bromine
or iodine to provide dyes of different colours. 4,10-
dibromoanthanthrone, also called vat orange 3 (Fig. 1,
compound 1b), is very popular in the dying industries as it
exhibits a bright, intense orange colour.
Fig. 2 Synthesis of anthanthrone 1a and its debrominated analogue 1b.
Although anthanthrone 1a and 4,10-dibromoanthanthrone
1b have been used in electronic devices, their poor solubility in
organic solvents makes them unsuitable for solution
processing. Thus, different strategies to functionalize them
have been developed with two purposes: 1) increase the
solubility by introducing alkyl chains and 2) modulate their
electronic properties by adding functional groups at the 4, 10,
6 and 12 positions. The presence of ketones and halogen
atoms on 4,10-dibromoanthanthrone provides two useful
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handles that open up many possibilities for functionalization.
View Article Online
In back-to-back reports in 2005 andDOI: 10.1039/C7TC03926C
2006, Neckers and
coworkers used 4,10-dibromoanthanthrone to prepare a series
of soluble anthanthrene derivatives by performing Suzuki-
Miyaura coupling with phenylboronic acid derivatives at the 4
Journal of Materials Chemistry C Accepted Manuscript
and 10 positions, followed by a functionalization at the 6 and
12 positions (Fig. 3).9,10 For the later derivatization, two
strategies were employed: the reduction of the ketones
followed by a dibromination and a Suzuki-Miyaura coupling
(path A, Fig. 3) or a direct functionalization with phenyllithium
derivatives followed by a dehydration of the resulting alcohol
with hydroiodic acid (path b, Fig. 3). Groups such as o-tolyl,
biphenyl, naphthyl, p-tert-butylphenyl and p-
trifluoromethylphenyl have been successfully introduced and
the resulting anthanthrene derivatives showed good
fluorescence properties in the greenish-blue region in solution
with fluorescence quantum yield values (ϕF) up to 33% have
been tested as emitters in OLEDs. Highly stable OLED devices
with half-lifetime of 3500 hours and a luminescence of ca. 600
cd/m2 have been obtained with these materials.
Fig. 3 Synthesis of 4, 6, 10, 12-tetraphenylanthanthrene derivatives 9,10
Different strategies for the functionalization of 4,10-
dibromoanthanthrone in the aim to explore the potential and
the limits of this building block for organic electronics have
been reported in 2013 (Fig. 4).11 The 4 and 10 positions were
reacted with different functional groups using palladium-
catalysed reactions such as Stille (16), Castro-Stephens-
Sonogashira (17) and Buchwald-Hartwig amination (18).
Interestingly, the nature of the substitutions at the 4 and 10
positions has a significant impact on the electronic properties.
For example, the presence of strong electron-donating
diarylamine groups, which create a strong intramolecular
donor-acceptor complex with the ketones, red-shifted the
absorption spectrum in solution by more than 120 nm
compared to the dialkyne (17) analogue.
The 6 and 12 positions can also be chemically transformed
to replace the ketones by functional groups of different
natures. For instance, the electron-withdrawing ketone groups
can be transformed into electron-donating alkoxy groups in
just one step using a reducing agent and alkyl halide (23).
When thiophene units are located at the 4 and 10 positions,
this transformation yields to a significant hypsochromic shift
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(ca. 75 nm) of the absorption spectrum and much higher
HOMO level. This example illustrates well how easy it is to
modulate the electronic properties of anthanthrone-based
molecules by simple chemical modifications. Other
transformations such as Ramirez dihaloolefination reaction to
introduce gem-dichloroolefins and eventually
bis(diarylethylene) (20),11 Knoevenagel condensations to
connect dicyanovinylene (22),11 amine condensation (21)12 and
nucleophilic substitutions to connect substituted alkynes (19)
all yield π-conjugated molecules with different electronic
properties.13,14 With this simple set of transformations,
materials with optical bandgap values varying from 1.43 to
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2.64 eV have been obtained in few synthetic steps.
Fig. 4 Overview of the functionalization reactions at the 4 and 10 positions (top)
and 6 and 12 positions (bottom) of the anthanthrone.
Anthanthrene- and anthanthrone-based devices showed
promising results in OFETs and OSCs, although only few
reports have been published on this topic in the last decade. In
2010, Sariciftci and coworkers published the OFETs
performances of a series of dye-based semiconductors,
including 4,10-dibromoanthanthrone (1b).15 Using a bottom-
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gate, top-contact device configuration, hole mobility values
View Article of
Online
up to μh = 1.9 x 10-3 cm2/Vs have been DOI:obtained
10.1039/C7TC03926C
with this
molecule as the semiconductor (vacuum deposition).
Interestingly, this molecule also exhibits electron transport
ability and OFET with μe = 8.8 x 10-3 cm2/Vs have been
Journal of Materials Chemistry C Accepted Manuscript
reported.16 Although these values are far from the best values
reported for OFETs, these studies showed that 4,10-
dibromoanthanthrone is a potential candidate for the
preparation of ambipolar semiconductors. The ambipolar
character of 4,10-dibromoanthanthrone (1b) has been
predicted recently in a theoretical study using density
functional theory (DFT) and molecular dynamics (MD)
calculations.17 Few years after these initial reports, hole
transport mobility of up to μh = 7.8 x 10-2 cm2/Vs for
anthanthrene derivatives with phenyl- and thiophene-
substituted anthanthrene derivatives have been reported (Fig.
5).18
Fig. 5 Anthanthrene derivatives used in bottom-gate, bottom-contact OFETs and
their transfer characteristics. 18 (Adapted from Ref. 18 with permission from The
Royal Society of Chemistry)
Because of their optical properties on the visible region,
anthanthrene- and anthanthrone derivatives have been tested
in OSCs application. In all the cases reported, these derivatives
have been used as the p-type materials in combination with
PC61BM or PC71BM. In only one synthetic step, Briseno and
coworkers prepared the 6,12-
bis(triisopropylsilylethynyl)anthanthrene from anthanthrone
1a and tested it in solution-processed bulk heterojunction
(BHJ) solar cells (Fig. 6).19 Without any thermal treatment on
the semiconductor film, they obtained a power conversion
efficiency (PCE) value of 1.95% with a fill factor (FF) value of
0.45%. In a similar study, the anthanthrene derivatives shown
in Fig. 5 (25-27) have been tested in bulk heterojunction OSCs.
In a simple ITO/PEDOT:PSS/Donor:PC61BM/LiF/Al
configuration, they obtained PCE values of up to 2.2% for
compound 25 under AM 1.5G illumination. In optimized
conditions, all three compounds yielded to PCE values above
1.0%, which is in the same range as other small molecules
tested as p-type materials in OSCs.20 The results obtained in
these studies are very encouraging considering that the
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anthanthrene derivatives tested absorb very little between
600 and 1000 nm, which represents the most important region
of the solar spectrum for solar cells applications.21
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Fig. 6 (a) Synthesis of 6,12-bis(triisopropylsilylethynyl)anthanthrene (TIPS-DBC).
(b) UV-vis spectra of TIPS-DBC in the solid state (black), TIPS-DBC/PC71BM (red)
and TIPS-DBC in solution (blue). (c) J-V characteristic of OSCs for TIPS-
DBC/PC71BM (1:1) blend at different annealing temperature. (d) EQE spectra of
the as-cast and annealed TIPS-DBC/PC71BM blends.19 (Reproduced from Ref. 19
with permission from The Royal Society of Chemistry)
Unsymmetrical anthanthrene derivatives have recently
been prepared and tested in dye-sensitized solar cells (DSSCs)
(Fig. 7).22 The donor and acceptor (anchoring) group have been
linked following the two possible paths of conjugation: the 4-
10 and the 6-12. It has been shown in a separate report that
these two axes are not equally efficient at extending the
conjugation of the anthanthrene core. 13 In general, the 6-12
axis provides better conjugation through the anthanthrene
core when an alkyne is used as spacer between the
anthanthrene and the π-conjugated units attached to it.
Single-molecule conductance measurements of two
acetynylpyridine-anthanthrene-acetynylpyridine triads using a
mechanically controlled break junction setup corroborate this
result. In fact, the triad with the acetynylpyridine units linked
at the 6 and 12 positions provides conductance values more
than 81 times higher than those measured for the triad linked
in the 4 and 10 positions.23 Unexpectedly, the compounds 29-
32 exhibit very similar λmax (~460 nm) and bandgap values,
regardless of the axis used for the donor-acceptor complex.
Moreover, the λmax values are unusually low (high bandgap) for
molecules possessing an intramolecular charge transfer
complex. One hypothesis is the high dihedral angle between
the π-conjugated units and the anthanthrene core that
prevent a good electron delocalization within the molecules.
Nonetheless, high PCE values (up to 5.27%) have been
obtained, meaning that a molecular design that would allow
optimal sunlight absorption in the low-energy region of the
solar spectrum, could provide even better efficiency.
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DOI: 10.1039/C7TC03926C
Journal of Materials Chemistry C Accepted Manuscript
Fig. 7 Symmetrical and unsymmetrical anthanthrene derivatives for DSSC
application.22
Anthanthrene and anthanthrone building blocks have also
been incorporated into the structure of π-conjugated
polymers. To the best of our knowledge, the first reported
example was published back in 1993 by Yi and coworkers who
copolymerized 4,10-dibromoanthanthrone (1b) with di(2-
thienyl)dimethylsilane using a palladium-catalysed Negishi
polymerization.24 The copolymer thus prepared exhibited very
low molecular weight (1400 g/mol), resulting in an unusually
low λmax value of 510 nm in THF, which corresponds to a red
shift of only 25 nm compared to the 4,10-
dibromoanthanthrone (1b).
In an attempt to obtain anthanthrone-based copolymers
with higher molecular weight, the anthanthrone unit was
substituted with 3-hexylthiophene at the 4 and 10 positions
prior to the polymerization reaction in order to increase the
solubility of the resulting polymer and thus avoiding rapid
precipitation in the reaction mixture (Fig. 8).25 This substitution
also allows the introduction of a halogen atom on both ends of
the unit, which is necessary for further palladium-catalysed
cross-coupling reactions. Starting from compound 33,
synthesized in three synthetic steps from 4,10-
dibromoanthanthrone 1b, a series of five copolymers has been
prepared through Stille coupling. Although copolymers with a
high density of alkyl chains (ex. PTANTDPP) possess moderate
Mn values (11600 g/mol), most of the polymers with
anthanthrone in the main chain possess relatively low Mn
values due to rapid precipitation in the reaction mixture.
Nonetheless, copolymers with broad absorption band in the
visible region (from 500 to 900 nm) and relatively low optical
bandgap (down to 1.39 eV in the solid state) have been
prepared. These polymers exhibit very interesting chromism
properties as they undergo fluoride-promoted photoinduced
electron transfer to form the radical-anion on the
anthanthrone unit. This has also been observed for electron-
deficient like naphthalene diimide with low-lying LUMO energy
level.26 The radical-anion and the dianion forms are easily
accessible through chemical doping in solution using sodium
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dithionite and that the reduction processes are reversible
upon exposure to air.
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Fig. 8 Synthesis and structures of anthanthrone-based copolymers and b) UV-
visible spectrum of the neutral, radical-anion and dianion form of the PTANTT.
Inset: dilute solution of PTANTT in the different redox states. 25 (Adapted with
permission from Ref. 25. Copyright 2015 American Chemical Society)
Fig. 9 Anthanthrene-based polymers and their performance in OFET and BHJ
OSC.27,28
Park and coworkers reported the synthesis of similar π-
conjugated polymers in which the anthanthrone is replaced by
its 6,12-dialkoxy analogue.27,28 This structural change ensures
better solubility of the resulting polymers, although their
redox properties are significantly changed since the quinoid
form is not available anymore to undergo a two-electrons
reduction process. The 4,10-dibromo-6,12-bis(2-
decyltetradecyloxy)anthanthrene was copolymerized with 2,2′-
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thiophenevinylenthiophene (PTVTC) and 2,2’-bithiopheneView Article Online
(PTTC) through Stille coupling (Fig. 9).DOI:
27,28 10.1039/C7TC03926C
The presence of
branched alkyl chains at the 6 and 12 positions provides a
much better solubility in common organic solvents and Mn
values of 52400 and 63200 g/mol were obtained for PTVTC
Journal of Materials Chemistry C Accepted Manuscript
and PTTC, respectively. Compared to the anthanthrone-based
polymers, PTVTC and PTTC exhibit slightly higher optical
bandgap values (~1.8 eV) while absorbing light in the 350 to
550 nm region (λmax ~ 400 nm). Both polymers have been
tested in OFETs and BHJ OSCs. For OFETs, charge mobility
values of μh ~ 10-4 cm2/Vs (bottom-gate/top-contact device
configuration) with Ion/Ioff ratio of ~104 have been measured
when the polymers are spin-coated on the substrate from a
chloroform solution. The PTTC-based devices exhibits slightly
better charge transport properties due to improve crystalline
ordering and larger crystalline domains in the thin films.
In BHJ OSCs, PCE values of 3.04 and 1.35% were obtained
for PTVTC and PTTC, respectively, when mixed with PC71BM.
Contrary to OFETs, the best efficiency was obtained for PTVTC
due to better phase separation with the PC71BM, leading to
better morphology of the thin film. Slightly better results (PCE
= 3.18%) was obtained for PTVTC when thermal annealing at
100 °C was performed, but not much difference has been
observed for PTTC. Interestingly, the later polymer yielded to
thermally stable solar cell devices as it retained 97% of its
initial efficiency at elevated temperature, proving the
morphological stability of the PTTC:PC71BM blend.
Fig. 10 (a) Deprotection of an anthanthrone-based trimer exhibiting
intramolecular H-bonding and b) XRD profile of the protected (black line) and
unprotected (red line) recorded as thin films on glass slide.12 (Adapted with
permission from Ref. 12. Copyright 2013 American Chemical Society)
One of the main disadvantages of anthanthrone as building
block for organic semiconductors is the steric hindrance at the
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4, 6, 10 and 12 positions. In fact, all these positions possess at
least one hydrogen atom at the peri position, forcing a large
dihedral angle between the anthanthrone core and the
neighbouring π-conjugated units. Thus, making low bandgap
anthanthrone-based materials with good solid-state
organization (with strong π-π interaction) at the molecular
level is very challenging. One way to decrease the dihedral
angle in π-conjugated molecules is to use functional groups
capable of doing intramolecular hydrogen or heteroatom
bonding between the units, providing conformational locks
and some rigidity.29 This strategy has been explored in the case
of anthanthrone by replacing the ketone groups at the 6 and
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12 positions by secondary amine (Figure 10).12 When
thieno[3,4-c]- pyrrole-4,6-dione (TPD) units are linked at the 4
and 10 positions, the dihedral angle goes from 52° for the Boc-
protected (34) derivative to 33° for the unprotected derivative
(35). This significant decrease of the dihedral angle is
attributed to the formation of a weak hydrogen bond (2.52Å)
between the carbonyl group (H-bond acceptor) of the TPD unit
and the secondary amine (H-bond donor) of the anthanthrone.
Although 33° is still quite high compared to other planar π-
conjugated systems, it is enough to decrease the optical
bandgap from 2.43 eV for the Boc-protected derivatives to
1.99 eV for the deprotected one. Moreover, the planarization
through H-bonding promotes molecular organization in the
thin film state as shown by X-ray diffraction recorded before
and after deprotection of the amine (Figure 10b).12
Fig. 11 Ir-catalysed borylation reaction of the anthanthrone at the 2 and 8
position and the corresponding macrocycles. Bottom left: X-ray structure of 6,12-
TIPSe (12,8)-[4]CA2,8.31 (Adapted from Ref. 31 with permission from The Royal
Society of Chemistry)
Although this strategy might seem potentially interesting
for the preparation of low bandgap, planar anthanthrone-
based molecules, it is quite limiting in regard to the chemical
diversity of the anthanthrone core since a very limited number
of functional groups allow such intramolecular interactions. To
overcome the presence of hydrogen atoms at the peri
positions and allow the synthesis of planar molecules and
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polymers without the need of using orienting Viewfunctional
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groups, linkage must be done at different DOI: 10.1039/C7TC03926C
positions. On the
anthanthrone, the only positions without cumbersome peri
hydrogen atoms are the 2 and 8 positions. As no 2,8-
difunctionalized anthanthrone derivatives are commercially
Journal of Materials Chemistry C Accepted Manuscript
available, regioselective C-H activation reactions have to be
used to introduce useful functional groups that will allow
further cross-coupling reaction. Based on their previous work
on phenacenes,30 Isobe and coworkers successfully performed
an Ir-catalysed direct borylation reaction of anthanthrene
derivative 28 at the least hindered 2 and 8 positions (Figure
11).31 The resulting diborylated molecule was used in a
Yamago Pt-catalysed macrocyclization to yield molecule 36.32
No optical characterization has been conducted on 36 and to
the best of our knowledge, no small molecules or polymers
have been prepared using the 2,8-functionalized anthanthrone
derivative. Nonetheless, the authors reported that the energy
gap between the planar and orthogonal conformer is about
2.24 kcal/mol for the dimer, which is very similar to
unsubstituted biphenyl.33 One can expect that connectivity at
the 2 and 8 positions using a five-membered ring heterocycles
such as thiophene, pyrrole or furan could lead to small
dihedral angles and consequently to planar, low bandgap
materials.
π-Conjugated molecules with a large carbon scaffold have
also been used as building blocks for the preparation of
supramolecular hosts, especially to encapsulate fullerenes and
their derivatives through π-π and charge transfer interactions.
Examples include porphyrins, coronenes and extended
tetrathiafulvalenes (exTTFs). Because of its large π surface,
anthanthrene is an ideal candidate for this purpose.
Anthanthrene can be made electron-rich through
functionalization, increasing its affinity for the electron-poor
fullerenes. In this line, a cavity-like host using anthanthrene
with tetrathiafulvalene (TTF) moieties attached at the 6 and 12
positions called superextended TTF (sExTTF, Figure 12) has
been prepared.34 In addition to increase the electron density,
the TTF units induce a curvature to the anthanthrene core due
to steric hindrance between the sulphur atoms of the TTF and
the hydrogen atoms in the peri positions (Figure 12b).34 This
curvature allows optimal concave-convex geometrical
matching between the host and the fullerene, increasing the
association constant of the complexes. Using a titration
experiment, association constants of up to 2.6 x 105 M-1 have
been measured with 40. Interestingly, sExTTF derivatives can
be oxidized back to the anthanthrone form through a
fullerene-sensitized photooxidation reaction under air.
Indanthrone and Flavanthrone
Indanthrone (2, vat blue 4) and flavanthrone (3, vat yellow
1) (Fig. 1) and their derivatives are vat dyes that contain
nitrogen atoms embedded within their sp 2 carbon skeleton.
The former possesses two secondary amine moieties that can
be functionalized with alkyl chains to increase the solubility of
its derivatives while the later has two imine groups that
provide the PAH core with relatively strong electron-
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withdrawing properties. Interestingly, these two vat dyes can
be prepared by thermal condensation of the same starting
material, namely 2-aminoanthraquinone, using alkaline
conditions at different temperatures.35
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Fig. 12 Synthesis of the superExtended TTF (sExTTF) host for fullerenes
complexation. Bottom-right: DFT-optimized structure of the sExTTF showing the
curvature of the anthanthrene core. 34 (Adapted with permission from Ref.34.
Copyright 2015 American Chemical Society)
The low solubility of indanthrone can be exploited to
prepare high-quality nanocrystals with very unique optical
properties. In their seminal work, Sariciftci and coworkers used
the Boc-protected indanthrone to prepare indanthrone
nanocrystals using a “hot injection” method similar to that
used for the synthesis of inorganic quantum dots.36 The basic
idea is to use a soluble Boc-protected precursor that is
deprotected thermally in a coordinating solvent in the
presence of an organic ligand (for the stabilization of the
nanocrytals), leading to the controlled precipitation of the dye
molecules and formation of nanocrystals (Figure 13).36 The
sizes and shapes of the nanocrystals can be controlled by the
growth conditions. From all the pigments used in this study,
indanthrone is the one presenting the most significant shift in
the optical properties as the Boc-protected indanthrone
absorbs light in the blue-green region (λmax = 475 nm) with an
optical bandgap of ca. 2.26 eV while indanthrone nanocrytals
absorb all over the visible range and exhibit a much lower
optical bandgap value (ca. 1.38 eV) (Figure 13b).36
Interestingly, indanthrone-based nanocrystals emit light in the
near-infrared region (λemi = ca. 1020 nm) making them
potentially interesting for biomedical applications.
Because of its low solubility in common organic solvents,
indanthrone is often tetraalkylated in similar conditions than
anthanthrone derivatives by reducing the carbonyl groups with
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sodium dithionite.37 In the process, the two secondary amines
View Article Online
are transformed into imines, thus creating DOI: 10.1039/C7TC03926C
a PAH with an
azaacene portion (portion in blue, Fig. 14), which is known to
induce high electron affinity and, consequently, good n-type
semiconducting properties.38 The resulting extended
Journal of Materials Chemistry C Accepted Manuscript
phenazine 42 derivative showed much lower band gap than
the straight phenazine (1.89 vs 2.91 eV) and exhibits efficient
green fluorescence in solution (ϕF = 56%).37,39 Guest-host-type
OLED made from compound 42 and poly(9-vinylcarbazole)
(PVK) showed luminance of up to 250 cd/m 2 and a luminous
efficiency of 1.0 cd/A.37 Later on, the same group reported that
a reduction of the alkyl chain length from C8 to C4 allowed an
increase of the electroluminescence efficiency with measured
luminance of 1670 cd/m2 in a PVK:42 matrix device.40
Flavanthrone and its derivatives have been mainly studied
as semiconductors in OFETs. In 2010, Sariciftci and coworkers
measured n-type mobility of μe = 0.012 cm2/Vs when
flavanthrone (3) was vacuum deposited on top of alternating
layers of guanine and adenine as the gate dielectric. 15,41 By
modifying the device geometry, they have been able to slightly
increase the mobility value to μe = 0.042 cm2/Vs.42
In order to modify the solid-state organization and the
electronic properties, Briseno and coworkers prepared a
flavanthrene derivative in a single synthetic step by treating
flavanthrone 3 with lithiated triisopropylsilylacetylene in THF
to give compound 43 (Fig. 15a).43 Interestingly, single crystal
transistors of this compound exhibit a relatively high mobility
of μh = 0.14 cm2/Vs. This high mobility value compared to
other TIPS-acetylene PAH tested in the same report can be
attributed to the 1D slipped-stack motif with close π-π
distance (3.38 Å) and π-surface overlap (18.3 Å2) (Fig. 15b,c).43
Fig 13 (a) Synthesis of indanthrone-based nanocrystals from a “hot injection”
method. b) Electron micrograph of the nanocrystals on a Si substrate. c)
Absorption spectrum of the Boc-protected indanthrone in solution (blue line)
and its nanocrystals (purple line). d) Emission spectrum of a colloidal dispersion
of indanthrone nanocrystals.36 (Adapted with permission from Ref.34. Copyright
2014 American Chemical Society)
Fig. 14 Synthesis of a tetraalkylated phenazine derivative from indanthrone.38
J. Name., 2013, 00, 1-3 | 7
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As they did with the indanthrone, Pron and coworkers
alkylated the flavanthrone with alkyl chains of different
lengths and tested the resulting green fluorescent compounds
in combination with PVK in OLED.44 Similarly to what they
obtained for indanthrone derivatives, they measured
luminance values of up to 1860 cd/m2 and luminous efficiency
values of 3.06 cd/A. It is worth mentioning that alkylated
flavanthrone derivatives exhibit much higher quantum yield
values than indanthrone (ϕF = ca. 80% vs ca. 60%).
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Fig. 15 (a) Synthesis of TIPS-acetylene flavanthrene 43. (b) π surface overlap
between stacks of 43. (c) packing motif of 43 between adjacent stacks view along
c-axis.43 (Adapted with permission from Ref.43. Copyright 2013 John Wiley and
Sons)
Other vat dyes
Other vat dyes have been used as building blocks for the
preparation of organic semiconductors, although at a much
lesser extent than the ones described above. Similarly to
anthanthrone, pyranthrone (4, Fig. 1) possesses two
conjugated ketone groups that could be functionalized to
provide conjugated molecules with promising charge transport
properties. In 2013, Briseno and coworkers prepared a
dialkynylated pyranthrene derivative from pyranthrone using
lithium TIPS-acetylide (Figure 16).43 Because of its larger π
conjugated network compared to the corresponding
anthanthrene derivative, a lower optical bandgap (2.27 eV vs.
2.47 eV) was obtained. However, no appreciable hole mobility
value has been measured for this molecule in OFET. In the
same article, they also reported the dialkynylation of other
dyes, including isoviolanthrone (45) and 7,14-
dibenzpyrenequinone (46 and 47) (Figure 16) for which they
measured hole mobility values of 6.7 x 10 -3 and 0.1 cm2/Vs,
respectively. TMS- and TIPS-acetylene-appended
dibenzpyrenequinone also showed promising light conversion
efficiency (η value up to 2.25%) when used as a donor in a
8 | J. Name., 2012, 00, 1-3
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solution-processed BHJ solar cells configuration inView
combination
Article Online
with PCBM.45 DOI: 10.1039/C7TC03926C
Journal of Materials Chemistry C Accepted Manuscript
Fig. 16 Alkynylated vat dyes used as semiconductors in OFETs.
Dibenzpyrenequinone has also been used to study the
influence of crystal polymorphism on the charge transport
properties of organic semiconductors. 46 Depending on the
conditions used for the crystals formation, a 1D slipped stack
or a 2D brickwork polymorph of compound 46 can be
obtained, resulting in very different charge transport ability.
While the red polymorph lead to hole mobility of 0.028
cm2/Vs, the yellow one, adopting a more suitable molecular
organizing for charge transport, exhibits mobility values up to
2.1 cm2/Vs, representing a 75-fold increase.
Violanthrone 7, or vat blue 20, and its derivatives have also
been studied as semiconductors for organic electronics. In
2011, Chen and coworkers reported hole mobility values up to
4.44 x 10-3 cm2/Vs for an O-alkylated derivative of 16,17-
dihydroxyviolanthrone (8, Fig. 1) in optimized conditions. 47
They show that the addition of a bad solvent (hexanes) to the
solution prior to the solution processing enhanced the mobility
value by one order of magnitude due to enhanced π
interactions in the solid state. One year after their initial
report, the same authors reported the photovoltaic properties
of three O-alkylated violanthrone derivatives.48 In a BHJ
configuration with PCBM as the n-type material, light
conversion efficiency ranging from 0.093 for the 2-ethylhexyl-
substituted derivatives to 0.54% for the hexyl-substituted one
have been obtained, which is quite low compared to other vat
dye-based semiconductors.
One of the most intriguing dyes regarding the electronic
and optical properties is vat brown 45 (9, Fig. 1). Structurally,
this dye is very different from the others as it contains an anti-
aromatic pentalene unit, providing the dye with very particular
optical properties, especially in the low energy region. Because
vat brown 45 is difficult to obtain through traditional chemical
suppliers, very few scientific articles have been published on
this dye and its functionalization. This might change soon as
Chi and coworkers developed a synthetic route to provide the
non-halogenated version of vat brown 45 (Fig. 17). 49 Their
strategy is based on a Pd-catalysed dimerization of a properly
functionalized phenyl-substituted alkyne (48) to give the
dibenzopentalene diester 49, followed by a double AlCl 3-
catalysed intramolecular Friedel-Craft acylation to yield the
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pentaleno-bis(anthracenequinone) (50). This compound can be
acetynylated using the conditions used for other vat dyes to
yield 51, a pentaleno-acene dimer with a low bandgap of 1.41
eV. Following the same synthetic strategy, a π-extended
version of 51 can be obtained starting from a naphthalene
derivative, providing compounds 52-54. The extension of
conjugation leads to a significant decrease of the bandgap by
0.24 eV at 1.17 eV for 54, which is the lowest ever reported for
a vat dye derivative. Compared to anthracene and tetracene
derivatives, the pentalene-fused acenes show much better
photostability. Moreover, 51 and 54 exhibit three quasi-
reversible oxidation waves and two quasi-reversible reduction
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waves by cyclic voltammetry, meaning that they could be good
ambipolar materials for OFET application. Combined with the
low bandgap value, these features make these derivatives very
promising candidates for organic electronics.
Fig. 17 (a) Synthesis of pentaleno-bis(anthracenequinone) and its π-extended
derivatives; (b) UV-visible spectrum of 51 and 54 in solution. 49 (Adapted with
permission from Ref.49. Copyright 2016 John Wiley and Sons)
Conclusions
This review article presented the recent development in the
area of vat dyes chemistry for organic electronics. Many
functionalization reactions have been developed for this
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specific class of molecules, allowing modulation ofView their optical
Article Online
DOI: 10.1039/C7TC03926C
and electronic properties. Several derivatives showed very
promising results in field-effect transistor and bulk
heterojunction solar cells. Nonetheless, it is safe to say that
the research in this area is still in its infancy as a very small
Journal of Materials Chemistry C Accepted Manuscript
portion of the chemical transformation available in the
chemists’ toolbox has been applied to the vat dyes. As for
traditional organic semiconductors, chemical modifications
leading to better morphological control and the continuous
fine-tuning of their electronic properties through proper
design are needed in order to make the vat dyes a credible
alternative to well-studied building blocks like thiophene,
carbazole and other heterocycles. Moreover, the portion of
existing vat dyes studied for organic electronics is still very low.
In fact, a large number of vat dyes remained unexplored,
mainly due to the lack of academic literature on these
molecules, which traditionally associated with the chemical
industry and low-tech applications. Figure 18 shows some
potentially interesting vat dyes for organic electronics that has
not been explored yet. With the increasing pressure to prepare
low-cost and efficient materials for electronic applications,
there are good chances that this will not be true for long and
that chemists will see the tremendous potential hiding behind
these molecules.
Fig. 18 Structures and names of potentially useful and unexplored vat dyes for
the preparation of π-conjugated organic semiconductors.
Acknowledgements
The author thanks the National Science and Engineering
Council (NSERC) of Canada.
Notes and references
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O
Br

Functionalization Organic
Br (Knoevanagel, alkynylation, semiconductors
SN2, amination, Pd-
O catalyzed cross-coupling,
olefination, etc.) OFETs
OLEDs
Commercial
OSCs
vat dyes