Progress in Polymer Science 38 (2013) 1815–1831

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Imide/amide based ␲-conjugated polymers for

organic electronics
Agnieszka Pron, Mario Leclerc ∗
Department of Chemistry, Université Laval, Quebec City, QC, Canada G1V 0A6

a r t i c l e i n f o a b s t r a c t

Article history: Recently, great progress has been made in the field of organic electronics. Such advance-
Received 7 January 2013 ments would not be possible without the synthesis of new donor–acceptor ␲-conjugated
Received in revised form 9 August 2013
polymers. In this review, we summarize recent developments in the preparation of
Accepted 13 August 2013
imide/amide containing polymers and their applications in bulk heterojunction (BHJ) solar
Available online 28 August 2013
cells and, to some extent, in organic field effect transistors (OFET).
© 2013 Elsevier Ltd. All rights reserved.
Keywords:
␲-Conjugated polymers
BHJ solar cells
OFET
Organic electronics
Donor–acceptor polymers

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1815
2. Thieno-[3,4-c]-pyrrole-4,6-dione (TPD) based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1816
3. Thieno[3,4-f]isoindole-5,7-dione (TID) based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1817
4. Phthalimide (Ph) based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1820
5. Bithiopheneimide (BTI) containing polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1822
6. Isoindigo (IID) based oligomers and polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1824
7. Thioisoindigo (TIID) based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1828
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1829
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1830
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1830

1. Introduction charge carrier mobility in organic field effect transis-

tors (OFETs) increased by three orders of magnitude, with
Over the last decade, significant progress has been made record values as high as 10.5 cm2 V−1 s−1 reported recently
in the field of organic electronics. Power conversion effi- by Liu and Ong [2].
ciencies (PCE) of polymer-based bulk heterojunction (BHJ) Such progress is a result of (i) advances in the under-
solar cells improved from 1% to over 10% [1]. Similarly, standing of the working principles of the devices and (ii)
the development of new, more suitable organic materials.
Each of the applications (i.e. solar cells, OFETs) requires
∗ Corresponding author. compounds with a specific set of both physical and elec-
E-mail address: mario.leclerc@chm.ulaval.ca (M. Leclerc). trochemical features. For example, when blended with

0079-6700/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progpolymsci.2013.08.007
1816 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
a fullerene derivative, conjugated polymers aimed as
p-type materials (donor) for organic solar cells should
have (i) HOMO energy level below −5.1 eV to ensure air
stability and effective charge separation at the polymer
donor:fullerene acceptor interface which results in high
open circuit voltage (Voc ); (ii) LUMO energy level in the
range of −3.7 to −4.0 eV to create enough driving force
to promote an exciton dissociation; and (iii) relatively
low optical band gap, between 1.2 and 1.9 eV, with a
broad absorption spectrum to absorb as much sunlight
as possible and to generate a high short circuit current
(Jsc ). Additionally they should be well soluble in common
organic solvents to warrant easy processability. On the
other hand, compounds suitable for OFETs should exhibit
strong ␲–␲ interactions as well as preferable edge-on
orientation in the solid state to promote high charge carrier
mobilities. In the search for polymers/oligomers fulfill-
ing such complex requirements, researchers prepared
hundreds of new materials.
There are two main approaches to achieve low band
gap conjugated polymers (see Fig. 1). The first one involves
incorporation of units which promote formation of quinoid
structure in the excited state [3]. As shown in Fig. 1a,
due to the strong aromatic character of benzene or thio-
phene rings, the percentage of quinoid structure in parent
poly(p-phenylene) 1.1 or polythiophene 1.2 is very limited.
However, the presence of fused ring systems, i.e. benzoth-
iophene 1.3 [3] or thienopyrazine 1.4 units (Fig. 1b), favours
the quinoid structure along polymer backbone as a result
of the competition in the aromaticity of both rings. The
second approach is based on the incorporation of alternat-
ing electron donating and electron accepting moieties in
the conjugated polymer backbone (Fig. 1c) [4]. This gives
rise to the intramolecular charge transfer interactions (ICT)
as a result of the overlap between HOMO orbitals local-
ized mainly on the electron rich unit and LUMO orbitals
localized mainly on the electron deficient unit. Fig. 1d
illustrates how HOMO and LUMO energy levels of the
polymer are influenced by electronic properties of the
monomers. HOMO energy levels derive from electron rich
unit, whereas LUMO energy levels are mainly influenced by
the choice of the electron deficient moiety. Thus, in order
to engineer optical band gap and HOMO–LUMO energy lev-
els, chemists can choose an appropriate combination of
electron rich and electron poor units from a wide library
of building blocks. The most promising electron deficient
units up to now are shown in Fig. 2.
Benzothiadiazole [5,6] (BTz) 1.5, naphto[1,2-c:5,6-c ]bis
[1,2,5]thiadiazole [7,8] 1.6, 3-fluorothieno[3,4-b]thien-2-
yl ketone [9] (TT) 1.7, diketopyrrolopyrrole [2] (DPP) 1.8,
naphthalenediimide [10] (NDI) 1.9, thieno-[3,4-c]-pyrrole-
4,6-dione [11] (TPD) 1.10, thieno-[3,4-f]-isoindole-6,7-
dione (TIN) 1.11, phthalimide (Ph) 1.12, bithiopheneimide
(BTI) 1.13, isoindigo (IID) 1.14 and thio-isoindigo (TIID)
1.15 based polymers have recently been successfully
incorporated into highly efficient devices. One can eas-
ily notice structural similarities between some of them.
Units 1.8–1.15 are relatively strong electron withdrawing
units due to the presence of amide/imide functional-
ity; they are symmetric, planar and rigid building blocks
prone to close ␲–␲ interactions. Their solubility can be
easily engineered by incorporation of various alkyl chains,
without sacrificing their electron accepting strength. The
goal of this review is to give readers an overview of the
␲-conjugated push–pull polymers/oligomers containing
amide/imide building blocks (1.10–1.15) with a special
emphasis on the structure–property relationships. Due to
the space limitations, DPP [12] (1.8) and NDI [10] (1.9)
based materials are omitted. However, comprehensive
reviews covering these subjects were recently published
in the literature [10,12].
2. Thieno-[3,4-c]-pyrrole-4,6-dione (TPD) based
polymers
In the search for electron deficient analogues of thio-
phene unit, one could think of incorporating nitro-, cyano-
or carbonyl-substituents in 3 and/or 4 position of the
thiophene ring. However, these approaches have sev-
eral drawbacks such as limited solubility of the resulting
polymers, steric hindrance and/or difficulties during poly-
merization process. On the other hand, imide containing
analogue, thus TPD (1.10) benefits from planarity and rigid-
ity of the structure which is prone to close ␲–␲ stacking.
Additionally, solubility of the resulting polymers can be
easily modified by incorporation of alkyl chain on nitrogen
atom. TPD monomer can be straightforwardly synthe-
sized from commercially available 3,4-dicarboxylic acid
thiophene. Recent advances in synthesis of TPD unit are
described elsewhere [13]. The first example of TPD based
polymer was published by Tour et al. [14,15] in 1997. Incor-
poration of this planar and electron deficient unit into
thiophene containing backbone resulted in low band gap
polymer 2.1 (Fig. 3). A comparison of its optical proper-
ties with those of monomeric structure 2.2 showed very
strong (153 nm) bathochromic shift of the earlier one. It
shows that ICT can be greatly enhanced by an extension
of conjugation and alternating arrangement of electron
rich and electron poor units. One of the most impor-
tant factors influencing optical and electronic properties
of the polymers is planarity. Planar polymer backbone
ensures good packing in the solid state due to good inter-
chain ␲–␲ interactions. Substituents at the 3-position of
polythiophene usually introduce steric interactions in the
head-to-head regioisomers which tend to twist the ring
causing a decrease in conjugation compared to regioregu-
lar head-to-tail polymer. In order to study the conformation
of two adjacent TPD units, Pomerantz and Leclerc groups
prepared TPD dimer 2.3 [16,17]. DFT calculations revealed
that despite the presence of carbonyl groups, the dimer
2.3 adopts an anti-coplanar conformation. This co-planar
conformation can be explained by favourable Coulombic
interactions between the partially negative carbonyl oxy-
gen atom of the TPD unit and the partially positive sulfur
atom of the adjacent thiophene ring. These results were
confirmed by X-ray crystal structure (Fig. 3b) which shows
a very short O S non-bonded distance of 2.9 Å, much
smaller than the sum of the oxygen and sulfur van der
Waals radii (3.32 Å).
Recently, several examples of push–pull polymers con-
taining TPD moiety has been published in the literature.
The most significant examples are shown in Fig. 4. An
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
Fig. 1. Approaches towards low band gap polymers: a, b – quinoid approach; c, d – donor–acceptor approach.
incorporation of benzo[1,2-b:4,5-b ]dithiophene (BDT) and
TPD units into polymer backbone resulted in formation of
2.5 [18–20]. An appropriate choice of alkyl substituents
ensures not only reasonably good solubility and pro-
cessability of the resulting materials but also strong
intermolecular interactions. PCE of 5.5% and 7.1% were
achieved for solar cells with 2.5/PC71BM as an active
layer without and with chloronaphthalene/diiodooctane,
respectively. The optical band gap of 2.5 is 1.78 eV. It was
predicted that higher PCE could be obtained with lower
band gap polymers due to the improved harvesting of
the light. Thus, various bridged bithiophene based poly-
mers were synthesized. PCE of 6.41% (Jsc = 14.1 mA cm−2 ,
Voc = 0.75 V) was obtained with carbon bridged 2.6 [21,22].
Comparison of the results achieved for 2.5 and 2.6 based
devices revealed higher Jsc of the later one due to the
smaller optical band gap. On the other hand, slightly lower
Voc of 2.6, can be explained by the higher HOMO energy
level. Next, Leclerc group replaced carbon atom by sil-
icon yielding 2.7 [23]. A PCE of 7.3% was recorded for
2.7 based devices. The better efficiency of silole-bridged
PDTSTPD polymer 2.7 compared to carbon bridged ana-
logues 2.6 (PDCPDTTPD) might be related to the improved
nanoscale morphology, most likely due to the presence of
C Si bonds which are longer than C C bonds. As a result,
the solubilizing side chains are displaced further from the
thiophene rings which allows stronger ␲–␲ interactions.
In order to further improve intermolecular interactions,
Reynolds et al. [24] substituted silicon by the larger ger-
manium atom (polymer 2.8). Computational studies show
that C Ge bond is indeed longer by 0.17 Å compared to C Si
bond. This places bulky substituents even further from the
1817
backone and should therefore result in better ␲–␲ inter-
actions. Direct comparison of 2.7 and 2.8 incorporated into
inverted solar cells revealed: (i) a higher short circuit cur-
rent for the germole analogue due to the lower band gap
of 2.8 and (ii) slightly lower open circuit voltage which is
in agreement with the higher HOMO level of 2.8. Recently
Reynolds et al. [11] achieved a PCE of 8.5% for inverted
solar cells with blend of 2.8:PC71 BM as an active layer.
Current studies indicate that upon further optimization of
the devices and/or increasing molecular weight of poly-
mers, efficiencies above 9% for both 2.7 and 2.8 should be
attainable in the near future. For detail comparison of vari-
ous TPD-based polymers, we redirect readers to the review
published recently [13].
3. Thieno[3,4-f]isoindole-5,7-dione (TID) based
polymers
Thieno[3,4-f]isoindole-5,7-dione unit (TID) 3.1 consists
of fused benzene and thiophene rings. Dearomatization of
the thiophene ring and formation of the quinoid structure
is accompanied by a gain of the aromaticity in the fused
benzene ring, resulting in energy band gap which is 1 eV
lower than that of polythiophene.
The first synthesis of TID was published in 2001 by
Wudl and co-workers [25]. The synthetic route, shown
in Scheme 1a, involves a Diels–Alder reaction of 3,4-
dimethyl butadiene and maleic anhydride, followed by
amination reaction to achieve 3.3 in almost quantitative
yield. The next steps involved sulfur-mediated oxidation
and bromination to furnish 3.5. It was then subjected to ring
closure and oxidation to yield 3.7. The last step involved
1818 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
Fig. 2. Examples of electron-accepting units.
Pummerer rearrangement to obtain compound 3.1.
Recently, Braunecker et al. [26] published much shorter
synthetic pathway towards 3.1. As shown in Scheme 1b,
thiophene-3,4-dicarboxyaldehyde 3.8 can be achieved in
two steps from commercially available thiophene-3,4-
dicarboxylic acid 3.9. The first step involves reduction of
3.9 with DIBAL-H to form alcohol, followed by oxidation
with pyridinium chlorochromate. Compound 3.1 was then
achieved via tributylphosphine catalyzed double conden-
sation between 3.8 and N-alkylmaleimide 3.11.
The first example of TID based homopolymer was also
published by Wudl and co-workers [25]. Ferric chloride
oxidative polymerization of 2-ethyl-hexyl substituted
TID resulted in polymer 3.12 (Fig. 5) with Mw = 88 kDa.
UV–vis-NIR measurements revealed optical band gap
of 1.24 eV. The smaller optical band gap compared to
TPD-based homopolymer 2.4 (1.8–1.9 eV) confirms the
stronger quinoid character of 3.12. In the search for
low-band gap materials, Wudl group prepared EDOT and
di-EDOT containing TID based polymers 3.13 and 3.14,
respectively [27–29]. Copolymer 3.13 was prepared via
Stille polymerization whereas 3.14 was synthesized via an
electropolymerization reaction. Due to the intramolecular
charge transfer interactions, the optical band gap of 3.13
and 3.14 was further lowered (1.0–1.1 eV) compared to
parent 3.12. Interestingly, these polymers are transparent
in the visible region and electrochemically stable during
p- and n-doping which make them perfect candidates for
near-infrared electrochromic device applications. Other
examples of TID based push–pull conjugated polymers
are shown in Fig. 5. Both polymers 3.15 and 3.16 were
prepared by Stille polymerization. Synthesis of polymer
3.15 was simultaneously published by the groups of Brau-
necker and Frechet [26,30,31]. Braunecker et al. reported
optical band gap of 1.43 eV whereas the Frechet group
prepared polymer with slightly higher optical band gap
(1.54 eV). The difference in the optical band gap could be
explained by the higher Mn of the polymer published by
Braunecker (Mn = 40 kDa vs. Mn = 19 kDa). One can easily
notice much lower band gap of 3.15 when compared to
its TPD based analogue 2.5. Direct comparison the HOMO
and LUMO energy levels of both polymers shows slight
increase of the HOMO level of 3.15 (−5.66 eV vs. −5.73 eV)
as well decrease of the LUMO level (−3.66 eV vs. −3.5 eV).
These findings are in good agreement with calculations
predicting HOMO destabilization and stabilization of
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831 1819

Fig. 3. Structures of TPD based compounds; (b) crystal structure of 2.3.

Fig. 4. Examples of TPD based polymers.

1820 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
Scheme 1. Synthetic pathways towards TID monomer.
LUMO with increased quinoidal character of the polymer
backbone. BHJ solar cell devices fabricated with 3.15/PCBM
blend exhibited PCE up to 3.0%. This somewhat low per-
formance compared to that of 2.5 can be attributed to an
unfavourable packing and morphology. DFT calculations
show that hydrogen atoms on the isoindole ring create
enough steric hindrance with the adjacent BDT unit to
induce a dihedral angle of >30◦ between units. This intro-
duces a significant twist of the polymer backbone, thus
decreases ␲–␲ interactions. On the other hand, the dihe-
dral angle in the case of 2.5 is close to 0◦ , allowing much
more effective ␲–␲ stacking. A similar trend was observed
when comparing dithienosilole-TID analogue 3.16 [32]
with 2.7. Lower optical band gap (1.46 eV vs. 1.76 eV) and
LUMO energy levels (−3.91 eV vs. −3.5 eV) are in agree-
ment with the stronger electron withdrawing character of
TID vs. TPD, as well as more favourable quinoidal structure.
Relatively low PCE of the device containing 3.16/PCBM
blend (PCE = 0.33%, Voc = 0.67 V, Jsc = 1.15 mA cm−2 ) can be
explained by a non-optimized morphology and the high
lying HOMO of polymer 3.16 (−5.26 eV).
4. Phthalimide (Ph) based polymers
Although phthalimide unit (1.12) was used for the
first time in conjugated polymers by Müllen et al. [33] to
prepare polyaniline analogues, it was the work of Watson
and Jenekhe [34] that introduced phthalimide based
polymers as suitable materials for organic electronics.
Polymers 4.1a and 4.1b (Fig. 6) bearing 2-ethylhexyl and
n-dodecyl substituents on the Ph unit were prepared via
Stille polymerization with Mn = 117 kDa and Mn = 207 kDa,
respectively [34]. A ∼50 nm red shift of the absorption
maximum was observed when comparing absorption
spectra in solution and in the solid state, which indicates
an increased backbone planarization and thus more
effective ␲–␲ stacking in the solid state.
The optical band gaps of polymers 4.1a and 4.1b are
1.72 and 1.64 eV, respectively. A PCE of 1.92% (Voc = 0.56 V,
Jsc = 6.15 mA cm−2 ) was recorded for 4.1b. Low Voc is the
result of the high lying HOMO energy levels (−5.2 eV)
which can be attributed to strong electron donating effect
of the alkoxy substituents on bithiophene unit. Interest-
ingly, thermally annealed blend films showed much lower
performance as the result of macroscale phase separation.
Recently, Jenekhe and Watson reported that an appropriate
use of (i) octanedithiol as an additive and (ii) fast dry-
ing conditions can result in much improved PCE of 4.1a
(4.09% vs. 0.43% without use of additives) [35,36]. Fast dry-
ing conditions (placing spin coated BHJ film in the vacuum
chamber at room temperature for 30 min) are intended
to freeze the phase segregated morphology in the early
stages. Additionally, polymers 4.1a and 4.1b were tested
in organic field effect transistors. Maximum hole mobili-
ties of 0.036 and 0.28 cm2 V−1 s−1 were recorded for these
polymers, respectively. The higher mobility of 4.1b can
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
Fig. 5. Examples of TID based polymers.
be attributed to better ␲–␲ stacking interactions due to
the presence of linear alkyl chain. Phthalimide-BDT con-
taining polymers 4.2 and 4.3 were prepared by Chen [37]
and Xie [38], respectively. A Mn = 20.7 kDa and PDI = 1.9
were reported for 4.2 synthesized via Stille polymeriza-
tion. Because of the relatively weak electron withdrawing
character of phthalimide moiety (Ph) compared to TPD unit
(2.5), 4.2 has a rather high energy band gap (2.15 eV) and a
fairly high lying LUMO energy level (−3.36 eV). The intro-
duction of additional 3-alkylthiophene units on the sides
of Ph unit resulted in formation of 4.3. Due to the pres-
ence of additional electron donating moieties, the HOMO
energy level of 4.3 is elevated by ∼0.18 eV when com-
pared to 4.2, whereas the LUMO energy level remains
unchanged. A PCE of 1.54% (Voc = 0.93 V, Jsc = 2.96 mA cm−2 )
was obtained for solar cell devices containing 4.3/PC71BM
blend as the active layer. Analogous structures, contain-
ing bi-thieno-fluorene (4.4) and bi-thieno-carbazole (4.5)
moieties as push units, were recently prepared by Moon
et al. [39] Both polymers were prepared with relatively
high Mn of ∼35 kDa. The combination of weak donor
and weak acceptor in the polymer backbone results in
materials with high energy band gap (∼2.4 eV) and high
LUMO energy levels (−3.2 to −3.1 eV). As a consequence,
a PCE of only 1.4% (Voc = 0.94 V, Jsc = 4.41 mA cm−2 ) was
achieved for carbazole containing 4.5. Low short circuit
current is most probably related to the large optical band
1821
gap which restricts photon harvesting as well as due to
the formation of large PC71BM domains in 4.5/PC71BM
blend as illustrated by AFM images. An incorporation of
unsubstituted bithiophene unit into phthalimide backbone
resulted in polymer 4.6. In order to maintain good solu-
bility of the polymer and to compensate the lack of alkyl
substituents on the donor moieties, Qin and coworkers
introduced bulky 2-octyldodecyl chain on the phthalim-
ide unit [40]. This allowed the preparation of 4.6 with a Mn
of 12 kDa. Optimized geometry of the polymer backbone
reveals the presence of a dihedral angle of ∼40◦ between
thiophene ring and phthalimide as a result of interac-
tions between the hydrogen atoms of the benzene ring
and the sulfur atom of the thiophene unit. Hole mobility of
5.3 × 10−3 mA cm−2 V−1 s−1 was recorded for this polymer.
Recently, Watson et al. [41] prepared polymers 4.7a–c
(Fig. 7) which consist of pyromellitic diimide (PMDI) unit
as an electron acceptor. Acetylene spacers were utilized
to improve planarity and therefore, the effective conju-
gation between acceptor and donor units. In order to
study the donating effect of electron rich moieties on
the opto-electronic properties of the resulting materials,
the authors chose 2,5-dialkyl (4.7a), 2,5-dialkoxy (4.7b)
and 2,5-diamino- (4.7c) substituted phenylene moieties as
donors. Their studies clearly indicate that an incorporation
of stronger donor has a huge impact on the HOMO energy
levels of the polymers. Deep HOMO energy level (−5.88 eV)
1822 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831

Fig. 6. Examples of Ph based polymers.

and fairly large optical bang gap of 2.31 eV were recorded
for 4.7a bearing weak electron donating moiety. In contrast,
values of −5.08 eV and 1.53 eV were confirmed for 4.7c.
LUMO energy levels remain unchanged. Polymers 4.7a–c
are excellent examples of how relatively small changes in
the chemical structure can alter the electronic properties
of the materials.
5. Bithiopheneimide (BTI) containing polymers
Bithiopheneimide (BTI) monomer (5.1) was introduced
in 2008 by Facchetti and Marks [42]. It can be easily
prepared from bithiophene-dicarboxylic acid 5.2 via con-
densation/cyclization with acetic anhydride to achieve
5.3, followed by condensation with amine (Scheme 2)
[42].

Fig. 7. Examples of PMDI based polymers.

A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831 1823

Scheme 2. Synthetic pathway towards BTI monomer.

Fig. 8. Examples of BTI based polymers.

Scheme 3. Synthetic pathway towards IID monomer.

1824 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
In the search for new n-type polymeric materials for
OFET, the authors prepared BTI-homopolymer 5.4 (Fig. 8)
[42]. An incorporation of long branched 2-octyldodecyl
chains enabled synthesis of 5.4 via Yamamoto polymer-
ization with Mn = 7.9 kDa. Incorporation of shorter chains
yielded in insoluble materials. Short ␲–␲ stacking distance
of 3.43 Å, a favourable solubilizing group orientation and
extremely high crystallinity of polymer film resulted in
electron mobility of 0.011 cm2 V−1 s−1 , and on/off ratio of
107 . Further optimization of device architecture resulted in
electron mobility as high as 0.2 cm2 V−1 s−1 [43].
Soon after, Marks group prepared donor–acceptor BTI-
containing polymers 5.5–5.8, shown in Fig. 8 [44,45].
Detailed comparisons of their optical and electrochemical
properties revealed that incorporation of stronger elec-
tron donating units (bithiophene vs. thiophene) leads to
a destabilization of LUMO energy levels (−3.22 eV for 5.7
vs. −3.33 eV for 5.5). More importantly, an increased elec-
tron donating capacity of quaterthiophene in the case of 5.8
results in higher HOMO energy level (−5.38 eV) when com-
pared to thiophene based 5.5 (HOMO = −5.55 eV). Studies
presented by Marks et al. indicate that by increasing the
conjugation length of donor blocks from thiophene (5.5)
to bithiophene (5.6) to quaterthiophene (5.8), the p-type
behaviour, thus hole mobility, becomes more pronounced.
BTI-containing polymers were also tested in BHJ solar cells.
Recently, power conversion efficiencies as high as 5.5% and
6.41% were achieved for BDT (5.9) [46] and dithienosilole
(DTS) (5.9) [47] based polymers, respectively. Comparisons
of the properties of polymers 5.9–5.10 with their TPD-
containing analogues 2.5 and 2.7 indicate small elevation of
HOMO energy levels of BTI series, due to the higher amide
group density on TPD unit as well as higher degree of back-
bone torsion in BTI series.
6. Isoindigo (IID) based oligomers and polymers
Although primarily introduced by Ciba, the first report
of using isoindigo (IID) based material in BHJ solar cells
was published by Reynolds group in 2010 [48]. Dibro-
moisoindigo 6.1 can be achieved via acid-catalyzed aldol
condensation and dehydration of commercially available
6-bromoisatin 6.2 and 6-bromooxindole 6.3, as shown in
Scheme 3. N-alkylation allows introduction of various alkyl
substituents to assure good solubility of the material.
Reynolds et al. [48] prepared two oligomeric structures
(Fig. 9) with general structure D–A–D (6.4) and A–D–A
(6.5) compromising isoindigo as electron acceptor unit
(A) and bithiophene moiety as electron donor (D). Both
oligomers exhibit broad absorption spectra through most
of the visible spectrum. Energy band gaps of 6.4 and 6.5
were estimated to be 1.67 and 1.76 eV, respectively. Cyclic
(CV) and square wave voltammogram (SWV) measure-
ments revealed HOMO and LUMO energy levels of −5.5 eV
and −3.9 eV for compound 6.4 and of −5.5 and −3.8 eV
for 6.5, respectively. The optoelectronic properties of these
compounds combined with good solubility, made them
perfect candidates for donor materials in BHJ solar cells.
When tested in photovoltaic devices, a PCE of 1.76%
(Voc = 0.74 V, Jsc = 6.3 mA cm−2 ) was recorded for spin
coated 6.4/PCBM blends after annealing. The performance
of 6.4 was later improved by using appropriate additives.
The authors demonstrated that use of polydimethylsilox-
ane (PDMS) increases Jsc , whereas triethylene glycol (TEG)
improves Voc due to the large hydrogen bonding param-
eters. As a result, a PCE of 3.3% was measured [49,50].
Triphenyl amine containing analogue of 6.4, namely 6.6,
with band gap of 1.69 eV and HOMO–LUMO energy levels
of −5.3 eV and −3.61 eV, respectively, was recently pub-
lished by Zou et al. [51] HOMO and LUMO energy values
are comparable with those of 6.4. A slight increase of the
HOMO energy level can be attributed to stronger electron
donating strength of triphenylamine compared to bithio-
phene. A maximum PCE of 0.84% was achieved for 6.6, with
relatively poor Jsc of 2.94 mA cm−2 , which can be related to
the low degree of intermolecular interactions.
Reynolds group prepared homopolymer 6.7 [52]
(Fig. 10) with a Mn of 29 kDa, via Suzuki polymerization.
This relatively high Mn can be attributed to the presence
of long, branched 2-hexyldecyl chains. Geometry opti-
mization via DFT methods indicated a dihedral angle of
34◦ between repeating units. Optical and electrochem-
ical characterization revealed HOMO and LUMO energy
levels at −5.54 and −3.84 eV, respectively. Additionally,
electrochemical measurements show high reversibility of
the reduction process. Generation of stable negative charge
carriers makes 6.7 a potential candidate as n-type mate-
rial for all-polymer BHJ solar cells. Indeed, initial studies
of P3HT/6.7 blend resulted in PCE of ∼0.5%. It is believed
that this value can be greatly improved after optimization
of devices.
In 2010, Reynolds et al. [53] utilized Stille and Suzuki
approaches to prepare a library of isoindigo-donor based
alternating polymers 6.9–6.14 (Fig. 11). Polymers 6.12 and
6.13 showed a low Mn due to their poor solubility. As
anticipated, optical and electrochemical measurements of
6.9–6.14 revealed that incorporation of stronger electron
donating moiety, i.e. PrDOT (6.14) instead of fluorene (6.9),
resulted in an increase of HOMO energy levels (−5.83 eV
vs. −5.68 eV) and in a decrease of HOMO–LUMO energy
band gaps (1.99 eV vs. 1.77 eV). Replacing fluorene (6.9)
by carbazole enabled Zou and He [54] to prepare poly-
mer 6.15 (Fig. 12). Due to the presence of only one
linear alkyl chain on carbazole unit, a rather low Mn of
9 kDa was obtained. The slightly stronger electron donat-
ing character of carbazole vs. fluorene resulted in stronger
donor–acceptor interactions and therefore, to a decrease
of the optical band gap by ∼0.2 eV (1.67 eV for 6.15). A PCE
of 0.4% was achieved for 6.15/PCBM blend. BDT-IID based
polymers 6.16a–b were prepared by the groups of Zou
[54] and Andersson [55]. A much lower Mn was achieved
for 6.16a bearing 2-ethylhexyl chains (Mn = 11 kDa) than
for 6.16b containing 2-hexyldecyl chains (Mn = 33 kDa)
on IID units, due to the better solubility of the mate-
rial during the polymerizaion process. To investigate
the effect of the thiophene spacers in IID-BDT struc-
tures, Andersson et al. prepared polymers 6.17 and 6.18,
shown in Fig. 12 [55]. Comparisons of their optoelec-
tronic properties indicate a small increase of the HOMO
energy levels in the case of 6.18, due to the presence
of stronger electron donor. Furthermore, the introduction
of additional alkyl substituents on the thiophene units
A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831 1825

Fig. 9. Examples of IID based structures.

Fig. 10. Examples of IID based polymers.

Fig. 11. Examples of IID based polymers.

1826 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831

Fig. 12. Examples of IID based polymers.

enabled a two-fold increase of the Mn . The investigation of
the performance of polymers 6.16–6.18/fullerene blends
in solar cells revealed higher efficiency for 6.17/PCBM
blends (PCE = 4.22%, Jsc = 7.87 mA cm−2 , Voc = 0.79 V). Inter-
estingly, a lower PCE (3.16%) was recorded when using
PC71BM as an acceptor. AFM imaging indicated the pres-
ence of smaller size domains and finer morphology in
the case of PCBM blends. DFT calculations performed by
Andersson group clearly indicate that additional unsubsti-
tuted thiophene rings between IID and BDT units increase
coplanarity of the polymer backbone (dihedral angle of
only 10◦ ) which is beneficial for the ␲–␲ stacking. One of
the limiting factors of polymers 6.16–6.18 is their rather
low absorption extinction coefficient. Recently, Zhang and
Sun [56,57] showed that IID-BDT based polymer 6.19 dis-
plays much stronger absorption in the entire visible region
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831 1827

Fig. 13. Examples of IID based polymers.

due to the additional conjugation in the alkyl-thienyl
substituted BDT units. The preliminary studies showed
promising PCE of 4.02%. Further optimization will most
likely lead to higher efficiencies.
Following the initial work of Reynolds, Andersson
[58–61] prepared IID-thiophene based polymer 6.20. The
presence of 2-hexyldecyl chains on IID unit enabled
preparation of the polymer with Mn as high as 86 kDa.
A power conversion efficiency of 3.0% (Voc = 0.89 V,
Jsc = 5.4 mA cm−2 ) was achieved for 6.20/PC71BM blend.
The authors discovered that this efficiency can be
improved by (1) using an appropriate donor:acceptor ratio,
(ii) addition of 2.5% of DIO and (iii) replacing PC71BM by
PC60BM. Such optimization resulted in a more efficient
charge carrier transport; indeed, Jsc increased two times.
Currently, the highest PCE (PCE = 6.3%, Jsc = 13.1 mA cm−2 ,
Voc = 0.7 V) for IID-based polymers was obtained for 6.21
by Andersson et al. [62].
A very detailed comparison of various IID-thiophene
based polymers was recently presented by Pei et al. (Fig. 13)
[60,63]. They prepared series of polymer containing cen-
trosymmetric (i.e. 6.22, 6.23 and 6.24) and axisymmetric
(6.20b, 6.25 and 6.26) donating units. DFT calculations,
mobility measurements, and morphology studies revealed
that polymers with centrosymmetric units exhibited better
crystallinity and lamellar packing in thin films, due to the
good interchain packing. According to authors’ “molecu-
lar docking” theory, small conjugated units (bithiophene
or biselenophene) can dock into the cavity formed by
large isoindigo cores, thus enhance ␲–␲ stacking. Indeed,
Pei et al. measured much higher mobility with centro-
symmetric copolymers 6.22 and 6.23 (mobility of 1.06 and
0.66 cm−2 V−1 s−1 , respectively) than for copolymers 6.25
or 6.26 (0.061 and 1 × 10−3 cm−2 V−1 s−1 , respectively). In
the meantime, Bao et al. [64] showed that the mobility
of bithiophene-IID analogues can be further improved by

Fig. 14. Examples of IID based polymers.

1828 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
Scheme 4. Synthetic pathway towards TIID monomer.
the incorporation of 1,1,1,3,5,5,5-heptamethyltrisiloxane
terminal unit on the IID unit (6.27), shown in Fig. 13. By
moving the branched site further away from conjugated
backbones, the backbones are allowed to come closer and
that leads to a better charge transfer. UV–vis absorption
measurements indicate different backbone configurations
for 6.22 and 6.27. The absorption maximum of 6.27 was red
shifted when comparing solution to the solid state mea-
surements, indicating additional planarization in the solid
state. On the other hand, a noticeable (∼16 nm) blue shift
was observed for 6.22. It is believed that due to the inter-
actions between the neighbouring bulky 2-octyldodecyl
chains, copolymer 6.22 has a more twisted backbone. It
was further proven by 2-D GIXS measurements which
indicated smaller ␲-stacking distance for 6.27 (3.58 Å)
than for 6.22 (3.75 Å). As anticipated, it resulted in the
increase of charge carrier mobility. Maximum mobility of
2.48 cm2 V−1 s−1 was measured for 6.27 after annealing at
170 ◦ C. The work of Bao shows that it is possible to achieve
a good balance between strong interchain interactions and
solubility/processability.
It is known from the literature, that an incorpora-
tion of planar heteroacenes into polymer backbone can
greatly improve ␲–␲ stacking thus result in better charge
carrier mobility. In the search for stable materials for
OFET, Zhang and Geng [65] prepared IID-dithienocarbazole
based polymer 6.28 and 6.29 (Fig. 14). Unfortunately, a
mobility of only ∼10−3 to 10−2 cm2 V−1 s−1 was mea-
sured for these polymers. It can be attributed to the fact
that both IID and dithienocarbazole are rather inflexible
units, resulting in poor self-assembly and low-ordering
of films.
7. Thioisoindigo (TIID) based polymers
Recently, Ashraf and McCulloch [66] prepared thio-
phene substituted isoindigo (TIID) monomer 7.1. As shown
in Scheme 4, it can be prepared in three steps from com-
mercially available 3-bromothiophene.
Suzuki polymerization of dibrominated 7.2 with ben-
zothiadiazole diboronic ester resulted in copolymer 7.3
(Fig. 15) [66]. The optical band gap of 7.3 was estimated to
be 0.92 eV, whereas this of IID analogue (6.8, Fig. 10) [52]
was 1.77 eV. This suggests much stronger donor–acceptor
interactions in the case of TIID building block when com-
pared to the IID moiety. More importantly, the presence of
thiophene units decreases the dihedral angle between the
units. Planarization of the structure was even more evident
in the case of BDT containing analogue 7.4 [67]. DFT calcu-
lations performed by Seki and Koizumi, indicated that the
dihedral angle of 23◦ between BDT and IID units in 6.16 was
reduced to 7–12◦ in 7.4, which results in more planar struc-
tures with extended conjugation. Up to now, maximum
hole and electron mobilities of 0.16 and 0.14 cm2 V−1 s−1 ,
respectively, were achieved for polymer 7.3.
Recent work of Janssen [68] on TIID-donor containing
polymers (7.5–7.7) suggests that reduction of the energy
band gap in the case of TIID based polymers when com-
pared to IID ones is due to the stronger electron-donating
properties of thiophene ring compared to that of benzene
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831 1829

Fig. 15. Examples of TIID based polymers.

thus raising of HOMO energy levels. This can potentially
limit applications of TII polymers in BHJ solar cells.
8. Conclusions
Nowadays, when designing new conjugated polymers,
polymer chemists have a large library of building blocks
to choose from in order to engineer optical band gap
and HOMO–LUMO energy levels of the resulting poly-
mer. In this regard the authors believe that amide/imide
based monomers presented herein are valuable part of
this collection. As general, they benefit from rigid and
co-planar structure as well as possibility to introduce var-
ious solubilizing groups. Their electron accepting abilities
vary from weak (i.e. phthalimide) to strong (i.e. isoindigo)
giving chemists even more choices. However, as shown
also in this review, preparing polymer with HOMO and
LUMO energy levels suitable, i.e. for solar cells application,
does not guarantee high performance. Indeed, it should be
considered as first step out of many, towards highly effi-
cient materials. Probably the most important, yet not fully
mastered, factor is solid state packing and film morphol-
ogy. It is necessary to balance between (i) high molecular
weight of polymer, (ii) good solubility thus processabil-
ity and (iii) close intermolecular interactions. The first two
are usually achieved via incorporation of long, branched
alkyl substituents which, on the other hand, disturb inter-
and sometimes also intra-molecular interactions, resulting
in very poor charge carrier mobilities. Finally, one could
notice strong tendency in academia towards achieving
higher and higher efficiencies (>10%). The use of complex
mixtures of additives, sophisticated techniques as well as
1830 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
monomers requiring long and costly synthesis becomes
very popular. The authors believe that in order to pro-
mote commercialization of organic electronics one should
consider (i) production cost, (ii) reproducibility and (iii)
stability over prolonged time.
Acknowledgment
A.P. thanks Dr. H. Norouzi-Arasi for the help in the
preparation of the manuscript and fruitful discussions.
References
[1] Anonymous. Solarmer Energy Inc. www.solarmer.com/ [accessed
August 2013].
[2] Li J, Zhao Y, Tan HS, Guo Y, DiC A, Yu G, Liu Y, Lin M, Lim SH, Zhou Y, Su
H, Ong BS. A stable solution-processed polymer semiconductor with
record high-mobility for printed transistors. Sci Rep 2012;754:1–9.
[3] Wudl F, Kabayashi M, Heeger AJ. Poly(isothianaphthene). J Org Chem
1984;49:3382–4.
[4] Havinga EE, TenHoeve W, Wynberg H. A new class of small band gap
organic polymer conductors. Polym Bull 1992;29:119–26.
[5] Park SH, Roy A, Beaupre S, Cho S, Coates N, Moon JS, Moses D, Leclerc
M, Lee K, Heeger AJ. Bulk heterojunction solar cells with internal
quantum efficiency approaching 100%. Nat Photon 2009;3:297–302.
[6] Sun Y, Takacs CJ, Cowan SR, Seo JH, Gong X, Roy A, Heeger AJ. Efficient,
air-stable bulk heterojunction polymer solar cells using MoOx as the
anode interfacial layer. Adv Mater 2011;23:2226–30.
[7] Osaka I, Shimawaki M, Mori H, Doi I, Miyazaki E, Koganezawa T,
Takimiya K. Synthesis and characterization, and transistor and solar
cell applications of a naphthobisthiadiazole-based semiconducting
polymer. J Am Chem Soc 2012;134:3498–507.
[8] Wang M, Hu X, Liu P, Li W, Gong X, Huang F, Cao Y.
Donor–acceptor conjugated polymer based on naphtho[1,2-c:5,6-
c]bis[1,2,5]thiadiazole for high-performance polymer solar cells. J
Am Chem Soc 2011;133:9638–41.
[9] He Z, Zhong C, Huang X, Wong WY, Wu H, Chen L, Su S, Cao Y.
Simultaneous enhancement of open-circuit voltage, short-circuit
current density, and fill factor in polymer solar cells. Adv Mater
2011;23:4636–43.
[10] Guo X, Kim FS, Seger MJ, Jenekhe SA, Watson MD. Naph-
thalene diimide-based polymer semiconductors: synthesis
structure–property correlations, and n-channel and ambipolar
field-effect transistors. Chem Mater 2012;24:1434–42.
[11] Small CE, Chen S, Subbiah J, Amb CM, Tsang SW, Lai TH, Reynolds JR,
So F. High-efficiency inverted dithienogermole-thienopyrrolodione-
based polymer solar cells. Nat Photon 2012;6:115–20.
[12] Nielsen CB, Turbiez M, McCulloch I. Recent advances in the devel-
opment of semiconducting DPP-containing polymers for transistor
applications. Adv Mater 2013;25:1859–80.
[13] Pron A, Berrouard P, Leclerc M. Thieno[3,4-c]pyrrole-4,6-dione-
based polymers for optoelectronic applications. Macromol Chem
Phys 2013;214:7–16.
[14] Zhang QT, Tour JM. Low optical bandgap polythiophenes by an
alternating donor/acceptor repeat unit strategy. J Am Chem Soc
1997;119:5065–6.
[15] Zhang QT, Tour JM. Alternating donor/acceptor repeat units in
polythiophenes intramolecular charge transfer for reducing band
gaps in fully substituted conjugated polymers. J Am Chem Soc
1998;120:5355–62.
[16] Berrouard P, Grenier F, Pouliot JR, Gagnon E, Tessier C, Leclerc M. Syn-
thesis and characterization of 5-octylthieno[3,4-c]pyrrole-4,6-dione
derivatives as new monomers for conjugated copolymers. Org Lett
2010;13:38–41.
[17] Pomerantz M. Planar 2,2 -bithiophenes with 3,3 - and
3,3 ,4,4 -substituents. A computational study. Tetrahedron Lett
2003;44:1563–5.
[18] Zou Y, Najari A, Berrouard P, Beaupré S, RédaAïch B, Tao Y, Leclerc MA.
Thieno[3,4-c]pyrrole-4,6-dione-based copolymer for efficient solar
cells. J Am Chem Soc 2010;132:5330–1.
[19] Zhang Y, Hau SK, Yip HL, Sun Y, Acton O, Jen AKY. Efficient poly-
mer solar cells based on the copolymers of benzodithiophene and
thienopyrroledione. Chem Mater 2010;22:2696–8.
[20] Piliego C, Holcombe TW, Douglas JD, Woo CH, Beaujuge PM,
Fréchet JMJ. Synthetic control of structural order in N-alkylthieno
[3,4-c]pyrrole-4,6-dione-based polymers for efficient solar cells. J
Am Chem Soc 2010;132:7595–7.
[21] Li Z, Tsang SW, Du X, Scoles L, Robertson G, Zhang Y, Toll F,
Tao Y, Lu J, Ding J. Alternating copolymers of cyclopenta[2,1-
b;3,4-b ]dithiophene and thieno[3,4-c]pyrrole-4,6-dione for high-
performance polymer solar cells. Adv Funct Mater 2011;21:3331–6.
[22] MacNeill CM, Peterson ED, Noftle RE, Carroll DL, Coffin RC. A
cyclopentadithiophene/thienopyrroledione-based donor–acceptor
copolymer for organic solar cells. Synt Met 2011;161:1137–40.
[23] Chu TY, Lu J, Beaupré S, Zhang Y, Pouliot JR, Wakim S, Zhou
J, Leclerc M, Li Z, Ding J, Tao Y. Bulk heterojunction solar
cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:2 ,3 -
d]silole copolymer with a power conversion efficiency of 7.3%. J Am
Chem Soc 2011;133:4250–3.
[24] Amb CM, Chen S, Graham KR, Subbiah J, Small CE, So F, Reynolds JR.
Dithienogermole as a fused electron donor in bulk heterojunction
solar cells. J Am Chem Soc 2011;133:10062–5.
[25] Meng H, Wudl FA. Robust low band gap processable n-type con-
ducting polymer based on poly(isothianaphthene). Macromolecules
2001;34:1810–6.
[26] Braunecker WA, Owczarczyk ZR, Garcia A, Kopidakis N, Larsen
RE, Hammond SR, Ginley DS, Olson DC. Benzodithiophene and
imide-based copolymers for photovoltaic applications. Chem Mater
2012;24:1346–56.
[27] Meng H, Tucker D, Chaffins S, Chen Y, Helgeson R, Dunn B, Wudl
F. An unusual electrochromic device based on a new low-bandgap
conjugated polymer. Adv Mater 2003;15:146–9.
[28] Sonmez G, Meng H, Wudl F. Very stable low band gap polymer for
charge storage purposes and near-infrared applications. Chem Mater
2003;15:4923–9.
[29] Scharber MC, Mühlbacher D, Koppe M, Denk P, Waldauf C, Heeger
AJ, Brabec CJ. Design rules for donors in bulk-heterojunction
solar cells—towards 10% energy-conversion efficiency. Adv Mater
2006;18:789–94.
[30] Douglas JD, Griffini G, Holcombe TW, Young EP, Lee OP, Chen MS,
Fréchet JMJ. Functionalized isothianaphthene monomers that pro-
mote quinoidal character in donor–acceptor copolymers for organic
photovoltaics. Macromolecules 2012;45:4069–74.
[31] Wu Y, Jing Y, Guo X, Zhang S, Zhang M, Huo L, Hou J. A thieno[3,4-
f]isoindole-5,7-dione based copolymer for polymer solar cells. Polym
Chem 2013;4:536–41.
[32] Li H, Sun S, Salim T, Bomma S, Grimsdale AC, Lam YM. Conjugated
polymers based on dicarboxylic imide-substituted isothianaphthene
and their applications in solar cells. J Polym Sci A: Polym Chem
2012;50:250–60.
[33] Dierschke F, Jacob J, Müllen K. A hybrid polymer of polyaniline and
phthalimide dyes. Synth Met 2006;156:433–43.
[34] Guo X, Kim FS, Jenekhe SA, Watson MD. Phthalimide-based polymers
for high performance organic thin-film transistors. J Am Chem Soc
2009;131:7206–7.
[35] Xin H, Guo X, Kim FS, Ren G, Watson MD, Jenekhe SA. Efficient solar
cells based on a new phthalimide-based donor–acceptor copolymer
semiconductor: morphology, charge-transport, and photovoltaic
properties. J Mater Chem 2009;19:5303–10.
[36] Xin H, Guo X, Ren G, Watson MD, Jenekhe SA. Efficient phthalimide
copolymer-based bulk heterojunction solar cells: how the processing
additive influences nanoscale morphology and photovoltaic proper-
ties. Adv Eng Mater 2012;2:575–82.
[37] Chen J, Shi MM, Hu XL, Wang M, Chen HZ. Conjugated polymers based
on benzodithiophene and arylene imides: extended absorptions
and tunable electrochemical properties. Polymer 2010;51:2897–
902.
[38] Zhang G, Fu Y, Zhang Q, Xie Z, Synthesis. Photovoltaic properties
of conjugated copolymers with benzo[1,2-b:4,5-b ]dithiophene
and bis(thiophene)phthalimide units. Macromol Chem Phys
2010;211:2596–601.
[39] Lee JY, Song KW, Ku JR, Sung TH, Moon DK. Development of DA-
type polymers with phthalimide derivatives as electron withdrawing
units and a promising strategy for the enhancement of photovoltaic
properties. Sol Energy Mater Sol Cells 2011;95:3377–84.
[40] Chen D, Zhao Y, Zhong C, Gao S, Yu G, Liu Y, Qin J. Effect of polymer
chain conformation on field-effect transistor performance: synthesis
and properties of two arylene imide based D–A copolymers. J Mater
Chem 2012;22:14639–44.
[41] Guo X, Watson MD. Pyromellitic diimide-based donor–acceptor
poly(phenylene ethynylene)s. Macromolecules 2011;44:
6711–6.
[42] Letizia JA, Salata MR, Tribout CM, Facchetti A, Ratner MA, Marks TJ. n-
Channel polymers by design: optimizing the interplay of solubilizing
 A. Pron, M. Leclerc / Progress in Polymer Science 38 (2013) 1815–1831
substituents crystal packing, and field-effect transistor characteris-
tics in polymeric bithiophene-imide semiconductors. J Am Chem Soc
2008;130:9679–94.
[43] Letizia JA, Rivnay J, Facchetti A, Ratner MA, Marks TJ. Variable tem-
perature mobility analysis of n-channel, p-channel, and ambipolar
organic field-effect transistors. Adv Funct Mater 2010;20:50–8.
[44] Guo X, Ortiz RP, Zheng Y, Hu Y, Noh YY, Baeg KJ, Facchetti A, Marks
TJ. Bithiophene-imide-based polymeric semiconductors for field-
effect transistors: synthesis, structure–property correlations charge
carrier polarity, and device stability. J Am Chem Soc 2011;133:
1405–18.
[45] Usta H, Facchetti A, Marks TJ. n-Channel semiconductor mate-
rials design for organic complementary circuits. Acc Chem Res
2011;44:501–10.
[46] Zhou N, Guo X, Ortiz RP, Li S, Zhang S, Chang RPH, Facchetti A, Marks
TJ. Bithiophene imide and benzodithiophene copolymers for efficient
inverted polymer solar cells. Adv Mater 2012;24:2242–8.
[47] Guo X, Zhou N, Lou SJ, Hennek JW, PonceOrtiz R, Butler MR,
Boudreault PLT, Strzalka J, Morin PO, Leclerc M, LópezNavar-
rete JT, Ratner MA, Chen LX, Chang RPH, Facchetti A, Marks TJ.
Bithiopheneimide–dithienosilole/dithienogermole copolymers for
efficient solar cells: information from structure–property–device
performance correlations and comparison to thieno[3,4-c]pyrrole-
4,6-dione analogues. J Am Chem Soc 2012;134:18427–39.
[48] Mei J, Graham KR, Stalder R, Reynolds JR. Synthesis of isoindigo-based
oligothiophenes for molecular bulk heterojunction solar cells. Org
Lett 2010;12:660–3.
[49] Graham KR, Mei J, Stalder R, Shim JW, Cheun H, Steffy F, So F, Kippelen
B, Reynolds JR. Polydimethylsiloxane as a macromolecular additive
for enhanced performance of molecular bulk heterojunction organic
solar cells. ACS Appl Mater Interfaces 2011;3:1210–5.
[50] Graham KR, Wieruszewski PM, Stalder R, Hartel MJ, Mei J,
So F, Reynolds JR. Improved performance of molecular bulk-
heterojunction photovoltaic cells through predictable selection of
solvent additives. Adv Funct Mater 2012;22:4801–13.
[51] Yang M, Chen X, Zou Y, Pan C, Liu B, Zhong H. A solution-processable
D–A–D small molecule based on isoindigo for organic solar cells. J
Mater Sci 2013;48:1014–20.
[52] Stalder R, Mei J, Subbiah J, Grand C, Estrada LA, So F, Reynolds JR. n-
Type conjugated polyisoindigos. Macromolecules 2011;44:6303–10.
[53] Stalder R, Mei J, Reynolds JR. Isoindigo-based donor–acceptor conju-
gated polymers. Macromolecules 2010;43:8348–52.
[54] Liu B, Zou Y, Peng B, Zhao B, Huang K, He Y, Pan C. Low bandgap
isoindigo-based copolymers: design, synthesis and photovoltaic
applications. Polym Chem 2011;2:1156–62.
[55] Ma Z, Wang E, Jarvid ME, Henriksson P, Inganas O, Zhang F, Andersson
MR. Synthesis and characterization of benzodithiophene-isoindigo
polymers for solar cells. J Mater Chem 2012;22:2306–14.
1831
[56] Cao K, Wu Z, Li S, Sun B, Zhang G, Zhang Q. A low bandgap poly-
mer based on isoindigo and bis(dialkylthienyl)benzodithiophene
for organic photovoltaic applications. J Polym Sci A: Polym Chem
2013;51:94–100.
[57] Hu C, Fu Y, Li S, Xie Z, Zhang Q. Synthesis and photovoltaic properties
of new conjugated polymers based on syn- and anti-benzodifuran.
Polym Chem 2012;3:2949–55.
[58] Wang E, Ma Z, Zhang Z, Henriksson P, Inganas O, Zhang F,
Andersson MR. An isoindigo-based low band gap polymer for effi-
cient polymer solar cells with high photo-voltage. Chem Commun
2011;47:4908–10.
[59] Vandewal K, Ma Z, Bergqvist J, Tang Z, Wang E, Henriksson P,
Tvingstedt K, Andersson MR, Zhang F, Inganäs O. Quantification
of quantum efficiency and energy losses in low bandgap poly-
mer:fullerene solar cells with high open-circuit voltage. Adv Funct
Mater 2012;22:3480–90.
[60] Lei T, Cao Y, Fan Y, Liu CJ, Yuan SC, Pei J. High-performance air-
stable organic field-effect transistors: isoindigo-based conjugated
polymers. J Am Chem Soc 2011;133:6099–101.
[61] Ma Z, Wang E, Vandewal K, Andersson MR, Zhang F. Enhance perfor-
mance of organic solar cells based on an isoindigo-based copolymer
by balancing absorption and miscibility of electron acceptor. Appl
Phys Lett 2011;99:143302–3.
[62] Wang E, Ma Z, Zhang Z, Vandewal K, Henriksson P, Inganäs O,
Zhang F, Andersson MR. An easily accessible isoindigo-based poly-
mer for high-performance polymer solar cells. J Am Chem Soc
2011;133:14244–7.
[63] Lei T, Cao Y, Zhou X, Peng Y, Bian J, Pei J. Systematic investigation
of isoindigo-based polymeric field-effect transistors: design strategy
and impact of polymer symmetry and backbone curvature. Chem
Mater 2012;24:1762–70.
[64] Mei J, Kim DH, Ayzner AL, Toney MF, Bao Z. Siloxane-terminated solu-
bilizing side chains: bringing conjugated polymer backbones closer
and boosting hole mobilities in thin-film transistors. J Am Chem Soc
2011;133:20130–3.
[65] Deng Y, Chen Y, Zhang X, Tian H, Bao C, Yan D, Geng Y, Wang
F. Donor–acceptor conjugated polymers with dithienocarbazoles
as donor units: effect of structure on semiconducting properties.
Macromolecules 2012;45:8621–7.
[66] Ashraf RS, Kronemeijer AJ, James DI, Sirringhaus H, McCulloch I. A
new thiophene substituted isoindigo based copolymer for high per-
formance ambipolar transistors. Chem Commun 2012;48:3939–41.
[67] Koizumi Y, Ide M, Saeki A, Vijayakumar C, Balan B, Kawamotov M,
Seki S. Thienoisoindigo-based low-band gap polymers for organic
electronic devices. Polym Chem 2013;4:484–94.
[68] VanPruissen GWP, Gholamrezaie F, Wienk MM, Janssen RAJ. Syn-
thesis and properties of small band gap thienoisoindigo based
conjugated polymers. J Mater Chem 2012;22:20387–93.