Indandione-Terminated Quinoids: Facile Synthesis by Alkoxide-Mediated Rearrangement Reaction and Semiconducting Properties

Article abstract of DOI:10.1002/anie.201911530

A series of 1,3-indandione-terminated π-conjugated quinoids were synthesized by alkoxide-mediated rearrangement reaction of the respective alkene precursors, followed by air oxidation. This new protocol allows access to quinoidal compounds with variable termini and cores. The resulting quinoids all show LUMO levels below ?4.0 eV and molar extinction coefficients above 10⁵ L mol^?1 cm^?1. The optoelectronic properties of these compounds can be regulated by tuning the central cores as well as the aryl termini ascribed to the delocalized frontier molecular orbitals over the entire molecular skeleton involving aryl termini. n-Channel organic thin-film transistors with electron mobility of up to 0.38 cm² V^?1 s^?1 were fabricated, showing the potential of this new class of quinoids as organic semiconductors.

Full text of DOI:10.1002/anie.201911530

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Accepted Article
Title: Indandione-terminated Quinoids:Facile Synthesis by Alkoxide-
mediated Rearrangement Reaction and Semiconducting
Properties
Authors: Yanhou Geng, Tian Du, Ruiheng Gao, Yunfeng Deng, Cheng
Wang, and Qian Zhou
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Angewandte Chemie International Edition
10.1002/anie.201911530
COMMUNICATION
Indandione-terminated Quinoids：Facile Synthesis by Alkoxide-
mediated Rearrangement Reaction and Semiconducting
Properties
[
a]
[a]
[a] [b]
[a]
[a]
[a] [b] [c]
Tian Du, Ruiheng Gao, Yunfeng Deng,*
Cheng Wang, Qian Zhou, and Yanhou Geng*
Dedication ((optional))
Abstract:
A series of 1,3-indandione-terminated -conjugated
quinoids were synthesized by alkoxide-mediated rearrangement
reaction of the respective alkene precursors, followed by
simultaneous air oxidation. This new protocol allows to access
quinoidal compounds with variable termini and cores. The resulting
quinoids all show LUMO levels below -4.0 eV and molar extinction
5
−1
−1
coefficients above 10 L mol cm . The optoelectronic properties of
these compounds can be regulated by tuning the central cores as
well as the aryl termini ascribed to the delocalized frontier molecular
orbitals over the entire molecular skeleton involving aryl termini. n-
Channel organic thin-film transistors with electron mobility of up to
2
−1 −1
0.38 cm
V
s
were fabricated, showing the potential of this new
class of quinoids as organic semiconductors.
Quinoidal compounds are of great interest because of their
[1]
unique electronic, optical, and magnetic properties. Most of the
reported quinoidal compounds are terminated by
dicyanomethylene moieties, which stabilize the quinoidal
scaffold by virtue of the strong electron-withdrawing ability of the
Figure 1. Reported methods and our new approach for the synthesis of
quinoidal compounds. Ar = aryl, Q = quinoid.
[
1b, 2]
cyano groups.
A commonly used method for accessing such
compounds involves palladium-catalyzed Takahashi coupling
reaction between aromatic halides and dicyanomethanide anion
[
4c, 5b, 5c]
[
3]
the lack of strong electron-withdrawing end groups.
followed by oxidation (Figure 1a), and various -conjugated
quinoidal compounds have been synthesized by this approach.
However, their termini are difficult to functionalize, which are
known to be as important as the quinoidal core in regulating the
Obviously, the limitations of the above synthetic routes have
created the need for new synthetic strategies to develop
quinoidal compounds whose center cores and termini can be
modified concurrently. In the current paper, we report a new
approach, i.e., alkoxide-mediated rearrangement reaction of
alkene precursors followed by air oxidation, to access termini-
and core-modified quinoids (Figure 1c). This protocol is
operationally simple and has a wide substrate scope. The
resulting compounds showed excellent stability and promising
semiconducting properties. Importantly, their properties can be
regulated by tuning the central core and the aryl termini.
[
1b, 3a, 3b, 4]
electronic properties of these compounds.
Another type
[
2b, 4b-d,
of quinoidal compounds is end capped by the aryl groups,
5
]
which can be synthesized by nucleophilic addition to a
carbonyl group followed by reduction (Figure 1b). The terminal
aryl groups of the resulting compounds can serve as handles for
the construction of quinoidal compounds with modifiable termini.
However, these quinoids suffer from limited central core units
[2b, 4b, 6]
and poor stability.
Additionally, their lowest unoccupied
The key intermediates in the synthesis of quinoidal
compounds are the aromatic moieties bearing a tertiary-carbon
at each end. It is known that the reaction between benzaldehyde
molecular orbital (LUMO) energy levels are rather high owing to
and phthalide in the presence of sodium methoxide (CH
give 2-phenyl-1,3-indandione in high yield, via rearrangement of
1-benzylidene-1,3-dihydroisobenzofuran intermediate
Scheme 1a). We hypothesized that this reaction could enable
3
ONa)
[
a]
T. Du, R. Gao, Dr. Y. Deng, C. Wang, Q, Zhou, Prof. Y. Geng
School of Materials Science and Engineering, Tianjin University,
Tianjin 300072, P.R. China
a
(
[
7]
E-mail: yunfeng.deng@tju.edu.cn (Y. Deng);
yanhou.geng@tju.edu.cn (Y. Geng)
Prof. Y. Deng, Prof. Y. Geng
the synthesis of di-tertiary-carbon-substituted aromatic
compounds, which could then be converted to quinoids by
oxidation. Therefore, we carried out the reaction of 4,4-
didodecyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-dicarboxal
dehyde (1a) and phthalide under the conditions shown in
Scheme 1b (Route A). Subsequent air oxidation did afford the
target compound 5a, but the yield was low (14%). Attempts to
improve the yield by optimizing the reaction conditions including
solvent, base, and oxidation reagent were unsuccessful (Tables
[
b]
c]
Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin
University and Collaborative Innovation Center of Chemical Science
and Engineering (Tianjin), Tianjin 300072, P.R. China
Prof. Y. Geng
Joint School of National University of Singapore and Tianjin
University, International Campus of Tianjin University, Binhai New
City, Fuzhou 350207, China
[
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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Angewandte Chemie International Edition
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COMMUNICATION
S1-S3). The formation of 5a should involve three steps:
To explore the scope of this new protocol, dialdehydes 1b-1f
with different sizes were selected to react with 2a under the
optimal reaction condition (Table 1). All the dialdehydes were
readily converted to the desired quinoids 5b-5f in reasonable
yields, and the yield was still as high as 44% (5f) when a
substrate with five-ring polycyclic core was used. The protocol
was also applicable for the synthesis of quinoidal compounds
with various substituents on the terminal phenyl rings. As shown
in Table 1, dimethoxyphenyl- and naphthyl-terminated
compounds 5g and 5h were obtained in yields of 56% and 41%,
respectively. However, the introduction of an electron-
withdrawing substituent, fluorine (F), chlorine (Cl), or bromine
(Br), on the terminal phenyl rings resulted in low yields (~10%) of
the corresponding products (5i-5k). We ascribed these inferior
results to the chemical instability of the F-, Cl-, and Br-
substituted phosphonates. However, by using stable
phosphonium salts 2d-2f instead, we were able to synthesize 5i-
5k in yields of >40%. Note that 5j and 5k were obtained as
mixtures of two isomers, owing to the asymmetry of the terminal
groups.
condensation, alkoxide-mediated rearrangement, and oxidation
[
7b]
(
Scheme 1b, Route A).
reaction to form 3 might be the limiting step for the synthesis of
a. Then we synthesized compound 3 separately by Wittig-
We inferred that the condensation
5
Horner reaction between 1a and phthalide-3-phosphonate (2a)
in 91% yield (Scheme 1b, Route B). Rearrangement reaction of
3
in the presence of sodium methoxide followed by simultaneous
air oxidation afforded 5a in 65% yield. The process of
rearrangement was confirmed by density functional theory (DFT)
calculations, which revealed that the rearrangement of 3 was
kinetically feasible (22.5 kcal/mol) and thermodynamically
favorable (42.7 kcal/mol) (Figure S1). We later found that the
isolation of 3 was unnecessary, and 5a could be readily obtained
from 1a and 2a in 70% yield over three steps (Scheme 1b,
Route B). Sodium hydride (NaH) was proved to be the best base
for the Wittig-Horner reaction of 1a and 2a after extensive
screening (Table S4).
The chemical structures of all the quinoidal compounds were
1
13
verified by H NMR and C NMR spectroscopy, high-resolution
matrix-assisted laser desorption ionization time-of-flight (MALDI-
TOF) mass spectrometry, and elemental analysis. Single-crystal
structure analysis can be used for unambiguous identification of
quinoidal compounds. Fortunately, single crystals of 5b and 5f
qualified for X-ray diffraction analysis were obtained by slow
diffusion of methanol into benzene or toluene solution. As shown
in Figure 2, the bond-lengths of C9-C10 and C11-C12 in 5b and
2
C6-C7 and C8-C9 in 5f are shorter than that of a typical C(sp )-
2
C(sp ) single-bond (ca. 1.45 Å) but are close to the length of a
2
2
typical C(sp )-C(sp ) double-bond (ca. 1.34 Å). While the bond-
lengths of C10-C11 and C12- C13 in 5b and C1-C6 and C7-C8
2
2
in 5f are longer than that of a typical C(sp )-C(sp ) double-bond.
This alternation in bond lengths unequivocally confirms the
[
5f, 8]
quinoidal framework of these compounds.
Scheme 1. Synthesis of 2-phenyl-1,3-indandione and 5a. Isolated yields are
reported.
a
Table 1. Substrate scope
a
Isolated yields are reported. 5b-5h were synthesized with phosphonates 2a-2c as the starting materials, and 5i-5k were obtained using phosphonium salts 2d-2f
as the starting materials. The yields in parentheses for 5i-5k were synthesized from phosphonates.
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Angewandte Chemie International Edition
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COMMUNICATION
compounds showed a reversible reduction process, indicating
that the anion species can be well stabilized by the quinoidal
skeleton. All the compounds showed low-lying LUMO levels of <
-
4.0 eV, which are comparable to those of the
[
1d, 3a]
dicyanomethylene-substituted quinoids.
Compounds 5a and
5b exhibited identical frontier molecular orbital (FMO) energy
levels, suggesting that the influence of the alkyl chains on the
[
10, 13]
FMOs was negligible.
As the -conjugation length of the
central core increased, the LUMO levels decreased from -4.06
eV for 5a to -4.27 eV for 5f, whereas the HOMO levels
increased from -5.70 eV for 5a to -5.27 eV for 5f (Figure 3c).
Compared with the HOMO level, the LUMO level is less
influenced by the central core, indicating that the bandgap
reduction is mainly caused by the increase of HOMO level as
the -conjugation extending. The FMO levels could also be
modulated by introducing various substituents on the terminal
phenyl rings (Figure 3d). Incorporating electron-rich methoxyl
groups increased the HOMO and LUMO levels, whereas
introducing electron-deficient F, Cl and Br groups decreased the
HOMO and LUMO levels. Compound 5i, which bears four F
atoms at the termini, had the lowest HOMO and LUMO levels at
Figure 2. ORTEP front view of 5b (a) and 5f (b) obtained from single-crystal
structures analysis. Alkyl chains and hydrogen atoms are omitted for clarity.
The numbers in red indicate bond lengths (Å).
The UV-vis-NIR absorption spectra of 5a-5k in toluene are
shown in Figure 3, and the related data are summarized in Table
S5. All the compounds showed well-structured absorption
spectra along with remarkably high molar extinction coefficients
-
5.43 and -4.38 eV, respectively. Interestingly, fused benzene
5
−1
−1
ring on the end groups (5h) gave rise to low LUMO level (-4.34
eV) and intact HOMO level (-5.28 eV), suggesting that
increasing the -conjugation length of the termini mainly
influenced the LUMO level. Clearly, the electronic properties of
the present quinoids could be finely tuned by modifying the
central cores and the termini. This feature is distinct from the
dicyanomethylene-terminated quinoidal systems, where these
properties can only be adjusted by turning the central core. In
addition, polymerization groups such as Br could also be
incorporated into these compounds, making them potentially
(
) of up to 2.4 × 10 L mol cm , which can be attributed to the
[
9]
rigid and planar nature of the quinoidal structure.
The
absorption maxima (max) were gradually bathochromic-shifted
from 610 nm for 5a and 5b to 790 nm for 5f upon extending the
-conjugation of quinoidal core (Figure 3a). The spectra of 5a
and 5b, which have the same central core, are almost identical,
indicating that the alkyl side chains had little effect on the
[10]
electronic structures of the molecules. The absorption spectra
of compounds with the same indaceno[1,2-b:5,6-b']dithiophene
(
IDT) core but different termini are depicted in Figure 3b.
[
1c, 14]
serve as building blocks for novel conjugated systems.
Introducing dimethoxy groups and halogen atoms or fusing
benzene ring on the terminal phenyl rings all gave rise to red-
shifted spectra. Compound 5h, which has the largest termini
2
.5
.0
5a
5f
5g
5h
(a)
2.5 (b)
5
5
b
c
2
(
naphthyl), showed the reddest spectrum with a max of 835 nm,
2.0
1.5
1.0
which is red-shifted by 45 nm compared with that of 5f. In
1.5
5d
5
i
5
5
e
f
5j
5k
comparison
counterparts,
to
their
dicyanomethylene-substituted
1.0
0.5
0.0
[
11]
5c and 5d showed max values that were red-
0.5
0.0
shifted by at least 75 nm, indicating that the present quinoidal
system has the potential for the construction of low-bandgap
conjugated molecules. This can be ascribed to the extended -
conjugation involving the terminal aromatic moieties. In fact,
DFT calculations indicated that both the highest occupied
molecular orbital (HOMO) and the LUMO were delocalized over
the entire conjugated framework (Figure S2). Notably, these new
quinoidal compounds were environmentally stable. Their UV-vis-
NIR absorption spectra remained unchanged when their
solutions were irradiated with UV light for 30 min (Figure S3),


500 600 700 800 900 1000
Wavelength (nm)
500 600 700 800 900 1000
Wavelength (nm)
-
-
-
-
-
-
3.5 (c)
-3.5 (d)
-4.0 -4.27 -4.18
-4.06 -4.07
-4.11
4.0
4.5
5.0
5.5
6.0
-4.24
-4.19
-4.34 -4.38 -4.32-4.35
-4.27
-4.5
5g
5
f
5f
5h 5i 5j 5k
5a
5b 5c 5d
5e
-5.0
-
5.11
-5.27
-5.5 -5.27
-6.0
-5.28
-5.35
-5.43
-5.39
-5.41
-
5.70 -5.70-5.62 -5.68
1
Figure 3. Solution UV-vis-NIR absorption spectra of 5a-5k in toluene (a, b)
and HOMO/LUMO levels of 5a-5k (c, d).
and their H NMR spectra did not change after their solutions
being stored in air for two months (Figures S4-S14). From
solution to film state, the max of 5a-5e were blue-shifted by 24 to
[
11b, 12]
91 nm, suggesting the formation of H-type aggregations.
In
Top-gate and bottom-contact (TGBC) organic thin-film
transistors (OTFTs) were fabricated to investigate the
semiconducting properties of these quinoids. No transistor
characteristics were observed for the devices based on 5a, 5b,
contrast, those of 5f-5k showed noticeable red-shifts due to the
[
11b,
formation of J-type aggregations (Figure S15 and Table S5).
1
2b]
This core-dependent aggregation behavior is also supported
by the single-crystal structure analysis of 5b and 5f (Figures S16
and S17). By tuning the central cores and the termini, the thin-
film optical bandgaps of these quinoids could be varied over a
wide range of 1.93-1.13 eV.
The electrochemical properties of 5a-5k were investigated by
solution cyclic voltammetry (CV) (Figure S18). All the
5d or 5g, whereas other compounds showed unipolar electron-
transport behavior as revealed by the clear off-regimes in their
[
15]
transfer curves (Figures 4, S19 and S20).
and transport were observed for the devices of 5c, 5e, 5f, 5h, 5i,
j and 5k although they showed relatively high-lying HOMO
No hole injection
5
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Angewandte Chemie International Edition
10.1002/anie.201911530
COMMUNICATION
levels (Figure S21). Similar phenomenon was observed in other Acknowledgements
[
4a]
quinoidal compounds, and the actual reason for the absence
of hole transport is unclear. Representative output and transfer
curves for the devices are shown in Figures 4, S19 and S20,
and their performance parameters are summarized in Table S6.
All the transfer and output characteristics showed negligible
hysteresis between forward and reverse sweeps, indicating low
This work was supported by the National Natural Science
Foundation of China (no. 21774093) and the National Key R&D
Program of “Strategic Advanced Electronic Materials” (no.
2016YFB0401100) of the Chinese Ministry of Science and
Technology. The DFT calculations by Dr. Yanfeng Dang was
deeply appreciated.
[
16]
trap density levels for electron transport.
electron mobilities (μ ) of 5c, 5e and 5f were 0.032, 0.0041 and
.28 cm V s , respectively. Fluorination of the terminal phenyl
groups enhanced the device performance and the μ of 5i
s . In contrast, 5h, 5j and 5k showed
The saturation
e
2
−1 −1
0
Keywords: Indandione • quinoidal compound • aromatic
dialdehydes • electron transport • organic thin-film transistor
e
2
−1
−1
reached 0.38 cm
V
2
inferior device performances with μ
V
e
of 0.13, 0.16 and 0.15 cm
s , respectively. The reliability factors (r) of the mobility
values were calculated according to the method proposed by
−
1
−1
[1]
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17]
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which are 67%, 76%, 80%, 86%, 81%, 82% and 73%
4
for 5c, 5e, 5f, 5h, 5i, 5j and 5k, respectively (Table S6).
Additionally, the device performance data in linear regime are
summarized in Table S6. The saturation and linear mobility
values were very close for these compounds. To evaluate the
device stability, electrical characteristics of 5i-based devices
were measured after storage for 30 days under ambient
conditions (Figure S22). The devices still operated effectively
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e
of 0.11 cm
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5
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[
18]
compounds.
VGS = 0 V to 80 V
-3
VDS = 80 V 0.018
VDS = 20 V
0.015
(
a)
10 (b)
0.20
0.15
0.10
0.05
0.00
VG = 10 V
-
4
80 V
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10
0
20 40 60 80
(V)
0
20 40 60 80
VGS (V)
V
DS
Figure 4. Output (a) and transfer (b) characteristics of the TGBC OTFT
devices based on 5i.
1159-1162.
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In conclusion, we have demonstrated a facile method for the
synthesis of 1,3-indandione-terminated quinoidal compounds
from readily accessible aryl dialdehydes and phthalide
derivatives. This new approach allows the access of termini- and
core-tunable quinoidal compounds and the feasible regulation of
their optoelectronic properties via central core and termini
engineering. These termini functionalized quinoids can also be
used as building blocks for novel conjugated systems.
Furthermore, OTFTs based on these compounds exhibited n-
channel characteristics with the highest electron mobility of up to
2
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0.38 cm
V
s . This study not only demonstrates a new
protocol for the synthesis of quinoidal compounds but also
provides a new class of organic semiconductors and new
building blocks for organic semiconductors.
[
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Entry for the Table of Contents
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T. Du, R. Gao, Y. Deng,* C. Wang, Q.
Zhou, Y. Geng*
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Three-step yields of 41-70% for 11 quinoids;
Properties adjustable via termini and core;
Unipolar n-type semiconductors.
Indandione-terminated Quinoids:
Facile Synthesis by Alkoxide-
mediated Rearrangement Reaction
and Semiconducting Properties
1
,3-Indandione-terminated quinoids with variable termini and central cores were
synthesized by alkoxide-mediated rearrangement reaction. The properties of these
quinoids can be regulated by tuning the central cores as well as the aryl termini.
These compounds displayed unipolar n-type semiconductor characteristics with
2
−1 −1
electron mobility of up to 0.38 cm V s .
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