Facile synthesis of thiophene/selenophene-fused acene and their optoelectronic properties

Article abstract of DOI:10.1016/j.tet.2017.10.072

Dibenzo thiophene- and selenophene are widely used in very different areas, ranging from biology to electronic engineering. However, their compounds require multiple synthetic steps. In this report, we introduce a two-step facile synthesis of a dibenzo thiophene/selenophene, namely diindeno[1,2-b:2′, 1′-d]thiophene-10, 11-dione (DITD) and diindeno[1,2-b:2′, 1′-d]selenophene-10, 11-dione (DISD). The compounds were further converted via a Knoevenagel condensation to dicyanovinylene derivatives. Their electronic and optoelectronic properties, backed by density functional theory (DFT) calculations are reported.

Full text of DOI:10.1016/j.tet.2017.10.072

Accepted Manuscript
Facile synthesis of thiophene/selenophene-fused acene and their optoelectronic
properties
Zitang Wei, Xiangchun Li, Fred Wudl, Yonghao Zheng
PII:
S0040-4020(17)31118-3
10.1016/j.tet.2017.10.072
TET 29075
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 9 September 2017
Revised Date: 24 October 2017
Accepted Date: 30 October 2017
Please cite this article as: Wei Z, Li X, Wudl F, Zheng Y, Facile synthesis of thiophene/selenophene-
fused acene and their optoelectronic properties, Tetrahedron (2017), doi: 10.1016/j.tet.2017.10.072.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
Facile synthesis of
thiophene/selenophene-fused acenes and
their optoelectronic properties
a,§
a,c,§
a,∗
a,b,∗
Zitang Wei , Xiangchun Li , Fred Wudl and Yonghao Zheng

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Facile synthesis of thiophene/selenophene-fused acene and their optoelectronic
properties
a,§
a,c,§
a,∗
a,b,∗
Zitang Wei , Xiangchun Li
, Fred Wudl and Yonghao Zheng
a
California NanoSystems Institute, University of California, Santa Barbara, CA 93106, USA.
b
School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054, China.
Center for Applied Chemistry, University of Electronic Science and Technology of China (UESTC), Chengdu 610054, China.
c
Key Laboratory for Organic Electronics and Information Displays (KLOEID) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation
Center for Advanced Materials (SICAM)Nanjing University of Posts & Telecommunications, Nanjing 210023, China
§
These authors contributed equally.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Dibenzo thiophene- and selenophene are widely used in very different areas, ranging from
biology to electronic engineering. However, their compounds require multiple synthetic steps. In
this report, we introduce a two-step facile synthesis of a dibenzo thiophene/selenophene, namely
diindeno[1,2-b:2’, 1’-d]thiophene-10, 11-dione (DITD) and
diindeno[1,2-b:2’,
Available online
1’-d]selenophene-10, 11-dione (DISD). The compounds were further converted via a
Knoevenagel condensation to dicyanovinylene derivatives. Their electronic and optoelectronic
properties, backed by density functional theory (DFT) calculations are reported.
Keywords:
Thiophene
Selenophene
2
017 Elsevier Ltd. All rights reserved.
Heterocycles
Knoevenagel condensation
Optoelectronic property
∗
∗
Corresponding author. E-mail address: wudl@chem.ucsb.edu (Fred Wudl)
Corresponding author. E-mail address: zhengyonghao@uestc.edu.cn (Yonghao Zheng)

2
Tetrahedron
ACCEPTED MANUSCRIPT
1
. Introduction
co-planarity of the molecular system so that it can allow an
efficient intermolecular π-π stacking in the solid state. At the
Heterocycles have been attracting a great deal of attention in
same time, the backbone is modified by adding the
electron-withdrawing dicyanovinylene functionality to the core to
remarkably depress the LUMO energy level without interrupting
the π-conjugation.
1,2
materials science. Thiophenes and selenophenes are widely
distributed in nature and are treated as important classes of
heterocycles due to their existence in a broad spectrum of natural
and synthetic organic compounds with multiple biological and
3
electronic properties. Over the decades, Thiophene- and
2. Results and Discussion
selenophene-containing compounds have drawn attention from
medicinal and synthetic chemists to explore different synthetic
4
The synthetic approach is shown in Scheme 1. BIT-OH2
reacted with benzenesulfonyl chloride to yield compound 1 as a
routes of thiophene and selenophene derivatives. Moreover,
relatively easy access of functional thiophene and selenophene
derivatives gives chemists opportunities to make use of
appropriated functionalized derivatives in various applications.
For example, the structural characteristic and substitution of
thiophene ring-containing drugs have an important impact on the
o
bright yellow solid at 0 C. During the reaction workup, we found
out that compound 1 starts decomposing before precipitating
from the reaction mixture. Once in the solid form, compound 1
becomes stable. The essential step for this molecular system was
the ring closure step to make the fused π-conjugated molecular
systems DITD and DISD. After intensive exploration of method,
solvent, temperature, reaction time, etc., sodium sulfide was
found to be the ideal sulfur source. The anhydrous sodium sulfide
was generated reduction of sodium and sulfur under reflux for 2
days in tetrahydrofuran (THF) with naphthalene as catalyst.
Compound 1 was dissolved in DCM, followed by a large excess
of anhydrous sodium sulfide. The reaction was stirred at room
temperature for 12 hours. A brown solid was collected and
analyzed to be compound DITD in 62% yield. The synthesis of
selenophene-based DISD followed the same steps as DITD,
resulting in 65% yield. It is worth to mention that we have tried
to introduce the sulfur/selenium source by using commercially
available Lawrenson/Woolings reagent, but the yield of products
from this approach were less than 20%.
5
metabolic pathways utilized for that drug. Also, thiophene-core
estrogen receptors show interesting binding affinity patterns that
6
may lead to significant superagonist activities. Additionally,
thiophene derivatives have huge applications as functional
7
8,9
materials in discotic liquid crystals, biosensors, organic field
1
0-12
effect transistors (OFETs),
organic light-emitting diodes
13,14
15-18
(OLEDs),
and organic photovoltaics (OPVs).
Several
synthetic routes for thiophene-
and
selenophene-containing molecules have been reported with
applications in different fields. Among them,
heteroaromatic-incorporated acenes are frequently involved.
Highly extended polyacenes have well-known applications in
19,20
organic electronics,
but large polyacenes are not chemically
19
stable under ambient conditions. Therefore, the introduction of
heteroatoms can help stabilize the backbone structures with
effects on the system’s electronic and solid-state structures. Most
of the existing synthetic routes of dibenzo heterocycles require
multiple, complicated steps. Several typical examples are shown
in Figure. 1, including synthesis of dibenzo[d,d’]thieno
2
1
[
[
3,2-b;4,5-b’]-dithiophene (DBTDT, 1), synthesis of benzo
22
1,2-b:4,5-b’]-dithiophene (BDT, 2),
benzo[1,2-b:4,5-b’]-
22
diselenophene (BDS, 3)
benzothiophene (BTBT, 4),
and [1]benzothieno[3,2-b][1]
and intramolecular cyclization of
fused thiophene derivative 5 and selenophene derivative 6. But
even today, the synthetic difficulties and cost are still issues that
limit the development of heteroacenes.
19
23
Scheme 1. Synthetic route for DITD, DISD, DITD-4CN and
DISD-4CN: i: triethylamine, pyridine, benzenesulfonyl chloride,
o
dichloromethane (DCM), 0 C; ii: Anhydrous Na S or Na Se,
2
2
DCM, room temperature; iii: titanium tetrachloride, pyridine,
malononitrile.
After the DITD and DISD compounds were synthesized and
characterized, the final step was to perform the Knoevenagel
condensation to add two dicyanovinylene units on the molecule.
However, the poor solubility of the DITD and DISD negatively
influenced the efficiency of the Knoevenagel condensation
Figure. 1. Examples of thiophene/selenophene based acenes.
We reported a gram-scale and column-free synthetic approach
for the thiophene- and selenophene-containing heteroacenes,
namely diindeno[1,2-b:2’,1’-d]thiophene-10,11-dione (DITD)
and diindeno[1,2-b:2’,1’-d]selenophene-10,11-dione (DISD)
(
Scheme 1). Even though the same reactions have been
performed for similar molecules, such as
dihydroindeno[1,2-b]fluorenone by Marks et al., truxenone by
27
2
8
29
Nielsen et al., diindenopyrazinedione by Yamashita et al., and
30
(Scheme 1) , based on a new intramolecular cyclization starting
pentaphenylenone by Maxine et al., moderate to low yield
reactions were reported because of either the steric hindrance of
the carbonyl groups or low reactivity.
with readily available [2,2’-Bi-1H-indene]-3,3’-dihydroxy
-1,1’-dione (BIT-OH2) that was first synthesized and
24
characterized over 100 years ago by Gabriel and Leupold.
The condensation was performed with the aid of titanium
tetrachloride, which is often used to activate the carbonyl units of
sterically hindered molecules. Under relatively mild conditions,
DITD, titanium tetrachloride, pyridine and large excess of
malononitrile were stirred in chloroform at room temperature for
Recently, BIT-OH2 derivatives have been synthesized and
25
characterized, such as BIT-zwitterion, and BIT-diester that
26
exhibited a highly efficient topochemical polymerization. We
further take advantage of the backbone of BIT-OH , bridging the
2
two indene units by sulfur or selenium atom to help establish the

3
2
4 hours to obtain purple solid DITD-4CN 30% yield. On the
The normalized absorption spectra of DITD-4CN and
ACCEPTED MANUSCRIPT
other hand, the Knoevenagel condensation with DISD was
slightly different from that of DITD, the reaction was refluxed in
chloroform for 2 hours and afforded DISD-4CN in 35%. The
structure of them has been adequately verified by MS, H NMR
and elemental analysis. Unfortunately, we were not able to get
DISD-4CN in dilute DCM solutions are shown in Figure 4. The
details of the photophysical properties of the compounds are
summarized in Table 1. Their UV-vis spectra showed two strong
absorption bands and one weak absorption band. The absorption
band in the region of 250-332 nm is attributed to the π-π local
electron transition of the benzene ending group ring. The
absorption band at longer wavelengths (332-400 nm) can be
1
*
13
the C NMR spectra of these four compounds due to their low
solubility.
*
assigned to the delocalized π-π excitation between the end group
We obtained crystals of all the molecules by slow evaporation
from DCM/ethanol solutions, but only those of DITD and
DISD-4CN were suitable for single crystal X-ray diffraction
benzene and thiophene or selenophene conjugated system. The
less pronounced band from 400 nm to 600 nm may be attributed
to the intramolecular charge transfer from the conjugated
skeleton to the electron-withdrawing cyano group. Moreover, the
absorption edge is red-shifted about 5 nm on going from
DITD-4CN to DISD-4CN. This assignment is also
well-supported by our theoretical calculations. The absorption
spectra of DITD and DISD were also obtained and are shown in
Figure S2.
(
Figure. 2). DITD crystallizes in an orthorhombic unit cell, space
group Pmn21, while DISD-4CN crystallizes in an orthorhombic
unit cell, space group Pccn. DITD is a completely flat molecule.
In contrast, the backbone of DISD-4CN remains almost coplanar.
But the two dicynanovinyl groups are forced to be out of plane
due to steric hindrance. Both systems showed a brick-wall
arrangement that is very promising to achieve high mobility
structures by increasing the dimensionality of charge transport
and rendering the systems less sensitive to charge traps.
According to the crystal structure of DITD, the π-π distance
between two molecules is 3.416 Å. On the other hand, the π-π
distance between two DISD-4CN molecules is 3.621 Å, which is
due to the out of plane CN groups. The stacking structures of
DITD and DISD-4CN are shown in Figure S1.
DITD-4CN
DISD-4CN
1.0
0
0
0
0
0
.8
.6
.4
.2
.0
300
400
500
600
700
Wavelength (nm)
Figure. 4. UV-Vis absorption of DITD-4CN and DISD-4CN in
dilute DCM solutions.
Figure. 2. Crystal structures of DITD (a) and DISD-4CN (b).
Thermal ellipsoids are shown at 50% probability level (purple,
red, yellow and green colors represent nitrogen, oxygen, sulfur
and selenium atoms, respectively). The hydrogen atoms are
omitted for clarity.
Electrochemical measurements revealed three pseudo
reversible reduction waves for DITD-4CN and DISD-4CN,
while no oxidation waves were observed in the solvent window.
(
Table 1 and Figure. 5). They exhibited rather closely spaced,
reversible electron reduction processes with a low onset
reduction potential that corresponds to a LUMO value of -3.81
eV, and -3.79 eV, respectively. The low onset reduction potential
suggests good electron accepting properties of the resulting
strong electron-withdrawing cyano groups, consistent with their
electron-deficient nature. Such a redox behavior is reasonable
considering the good electron-accepting ability for the S or
Se-annulated skeleton, making the system more susceptible to
reduction (n-doping) rather than oxidation (p-doping). Moreover,
the solution optical band gaps were 2.03 and 2.01 eV,
respectively. These trends are consistent with the results of
theoretical calculations.
To better understand the role of S or Se-annulated compounds
with and without dicyano-substitution, density functional theory
(DFT) calculations and photophysical experiments were
performed on all the molecules. Optimized geometries showed
planar linear structure in DITD, DISD, DITD-4CN and
DISD-4CN which are preferred for π-π stacking. In all the
molecules, the HOMO and LUMO frontier molecular orbitals
were delocalized throughout the thiophene or selenophene
conjugated skeleton, with the exception of DITD-4CN and
DISD-4CN, where the LUMO orbitals are mainly localized on
the dicyanovinylene-group (Figure. 3). The HOMO-LUMO
energy gaps of DITD-4CN and DISD-4CN were found to be in
the range of 2.89 eV and 2.80 eV, respectively.
DITD-4CN
DISD-4CN
+
Fc
-
1.5 -1.0 -0.5 0.0 0.5+ 1.0
Potential (V vs. Ag/Ag )
Figure. 5. Cyclic voltammetry of DITD-4CN and DISD-4CN
+
Figure. 3. Frontier molecular orbitals and HOMO-LUMO gaps.
(DCM/0.1 M TBAPF vs. Ag/Ag at 100 mV/s).
6

4
Tetrahedron
o
1
Table 1. Photophysical and electrochemical properties of DITD,
DISD, DITD-4CN and DISD-4CN.
Mp: >260 C. H NMR (600 MHz, CDCl , δ, ppm): 7.90 (dd, J =
ACCEPTED MANUSCRIPT
3
8.0, 1.4 Hz, 4H), 7.41 (td, J = 7.4, 1.1 Hz, 2H), 7.35 (d, J = 6.6
opt
λabs (nm)
λonseta Eg
E
(eV)
E
(eV)
Hz, 2H), 7.32 (t, J = 7.3 Hz, 2H), 7.25-7.19 (m, 8H). MS (m/z):
Calcd for MS: 570.59, Found: (M ) 571.92. Anal. Calcd for
LUMO
HOMO
b
c
d
+
(
nm) (eV)
DITD
DISD
276, 439
277, 293, 453
DITD-4CN 305, 349, 531
DISD-4CN 309, 354, 541
485
503
610
616
2.56
-3.49
-3.37
-3.81
-3.79
-6.05
-5.83
-5.84
C
30
H
18
O
8
S
2
: C, 63.15; H, 3.18; S, 11.24. Found: C, 63.91; H,
2
.81; S, 11.92.
2.46
2.03
2.01
4
.2.2 Synthesis of Na2S
-5.80
a
b
All glassware and stir bars were dried in the oven at 140 ºC
λonset was the onset for the solution absorption spectra. Eg
for several hours. 14.0 g of sodium was added into 50 mL of dry
THF with 3.0 g of naphthalene as catalyst. 9.6 g of sulfur was
then added to the suspension and the mixture was heated to
reflux for 12 hours under nitrogen gas protection. Thus a white
solid, sodium sulfide was formed and washed with dry THF.
(
optical energy gap) calculated from the absorption onset of
c
d
solution spectra. Obtained from CV data. Obtained from the
ELUMO (CV data) - optical band gap (Eg ).
opt
3
. Conclusion
In summary, we have applied a facile and simple gram-scale
4.2.3
Synthesis
of
diindeno[1,2-b:2’,1’-d]
synthetic procedure for a unique planar, π-extended S or
Se-annulated building block. Based on the linear molecules, a
novel series of tetracyano-substituted S and Se-annulated
derivatives have thus been facilely constructed. The optical and
electrochemical properties were investigated to understand the
role of the structure on functional properties of the resultant
molecules. The results showed unique optoelectronic
characteristics with wide optical band gaps and redox-active
properties. The interesting structural and electronic properties of
the novel planar, π-extended S or Se-annulated building block as
the skeleton reported herein hold promise for potential
applications of in the field of molecular electronics.
thiophene-10,11-dione (DITD)
1
.10 g (1.93 mmol) of compound 1 was added in a 500 mL
round-bottom flask with 200 mL of DCM. 260 mg of sodium
sulfide was added and the mixture was stirred for 12 h. Purple
solid was formed and filtered, washed with methanol multiple
times and dried with vacuum to yield 0.34g of DITD (62%
yield). Mp: >260 C. H NMR (600 MHz, CDCl , δ, ppm): 7.53
d, J = 7.2 Hz, 2H), 7.39 (t, J = 7.0 Hz, 2H), 7.23 (d, J = 7.9 Hz,
H), 7.16 (d, J = 7.3 Hz, 2H). MS (m/z): Calcd for MS: 288.02,
Found: (M ). 289.48. Anal. Calcd for C H O S: C, 74.99; H,
.80; S, 11.12. Found: C, 75.78; H, 2.01; S, 12.01.
o
1
3
(
2
+
18
8
2
2
4
.2.4 Synthesis of DITD-4CN
4
. Experimental
0
.50 g (1.74 mmol) of DITD was put into 160 mL of
4
.1. General
chloroform in a 500 mL round-bottom flask. 3.03 g of
malononitirle and 8 mL of pyridine was added as well. Then 0.64
mL of titanium tetrachloride was added dropwise into the flask
with stirring at room temperature for 24 hours and the precipitate
was filtered and washed with methanol. The product DITD-4CN
was formed as a dark purple solid (0.20 g, 30%). Mp: >260 C.
H NMR (600 MHz, CDCl , δ, ppm): 8.17 (d, J = 7.7 Hz, 2H),
.43 (t, J = 7.6 Hz, 2H), 7.31 (dd, J = 16.0, 7.8 Hz, 4H). MS
m/z): Calcd for MS: 384.05, Found: (M ). 384.93. Anal. Calcd
Unless otherwise stated, all of the chemicals were purchased
from Aldrich Chemical and used as received. When necessary,
solvents and reagents were purified using standard procedures.
All manipulations involving air-sensitive reagents were
o
1
performed under an atmosphere of dry nitrogen. H NMR spectra
1
3
were recorded on a Varian Inova600 spectrometer. Absorption
spectra were taken on a Varian Cary 50 ultraviolet-visible
spectrometer. Single crystal X-ray diffraction was carried out
7
(
+
for C H N S: C, 74.99; H, 2.10; N, 14.57; S, 8.34. Found: C,
5.09; H, 2.18; N, 13.18; S, 7.03. UV-vis (DCM) λmax nm (ε):
05 (277944), 349 (106890), and 531 (7508).
24
8
4
using
a
Bruker Kappa Apex diffractometer with
7
3
graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at a
temperature of 100 K. Mercury software was used to process the
raw data. Electrochemical measurements were performed with a
Princeton Applied Research Potentiostat/Galvanostat model
4.2.5 Synthesis of Na
All glassware and stir bars were dried in the oven at 140 ºC
for several hours. 14.0 g sodium was put into 50mL dry THF
with 3.0 g naphthalene as catalyst. 23.7 g selenium was then
added to the suspension and the mixture is heated to reflux for 9
hours under nitrogen gas protection. Thus, a white solid, sodium
selenide was formed and washed with dry THF.
Se
2
2
63A. The electrochemical measurements were carried out in
DCM solution containing 0.1 tetrabutylammonium
hexafluorophosphate as the supporting electrolyte, with a
platinum disc, platinum wire, and silver wire as the working,
counter, and pseudo-reference electrodes, respectively.
ferrocene-ferrocenium (Fc/Fc ) redox couple was used as an
internal standard (4.80 eV below the vacuum level).
M
A
+
4.2.6
Synthesis
of
diindeno[1,2-b:2’,1’-d]selenophene-10,11-dione (DISD)
4
4
.2. General Procedures
1
.10 g (1.93 mmol) of compound 1 was added in a 500 mL
.2.1 General procedure for the preparation of compound 1
BIT-OH2 (2.00 g, 6.94 mmol) was suspended in a 2 L
round-bottom flask with 200 mL of DCM. 260 mg of sodium
selenide was added and the mixture was stirred for 12 h. A dark
purple solid was formed and filtered, washed with methanol
multiple times and dried with vacuum to yield 0.42 g of DISD
round-bottom flask in 250 mL of dry DCM and 2 mL of
triethylamine under nitrogen atmosphere. The reaction mixture
was cooled to 0 ºC in a salt ice bath. Benzenesulfonyl chloride
o
1
(
yield 65%). Mp: >260 C. H NMR (600 MHz, CDCl , δ, ppm):
3
7
.51 (d, J = 7.2 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.23 (d, J = 8.0
(3.5 mL, 27.43 mmol) was combined in a separate flask with 2
Hz, 2H), 7.13 (d, J = 7.3 Hz, 2H). MS (m/z): Calcd for MS:
mL of DCM and 1 mL of pyridine. This mixture was added
dropwise to the reaction solution, which turned dark yellow.
After stirring for 10 minutes at 0 ºC the reaction was quenched
+
3
6
35.97, Found: (M ). 336.96. Anal. Calcd for C H O Se: C,
18 8 2
4.49; H, 2.41. Found: C, 65.04; H, 2.02.
1
00 mL of methanol and an orange precipitate was observed. The
4
.2.7 Synthesis of DISD-4CN
solids were filtered, washed with methanol multiple times, and
dried under vacuum to yield 2.45 g of compound 1 (62% yield.)

0
.50 g (1.49 mmol) of DISD was put into 160 mL of
18. Nielsen, C. B.; Holliday, S.; Chen, H.-Y.; Cryer, S.
J.;5
ACCEPTED MANUSCRIPT
McCulloch, I. Acc. Chem. Res., 2015, 48, 2803-2812.
chloroform in a 500 mL round-bottom flask. 3.03 g of
malononitirle and 8 mL of pyridine was added as well. Then 0.64
mL of titanium tetrachloride was added dropwise into the flask
with stirring. The mixture was heated in oil bath for 2 hours and
the precipitate was filtered and washed with methanol. The
product DISD-4CN was formed as a dark purple solid (0.23 g,
5%). Mp: >260 C. H NMR (600 MHz, CDCl , δ, ppm): 8.16
d, J = 7.6 Hz, 2H), 7.42 (t, J = 7.3 Hz, 2H), 7.35-7.27 (m, 4H).
MS (m/z): Calcd for MS: 431.99, Found: (M ). 432.04. Anal.
Calcd for C H N Se: C, 66.83; H, 1.87; N, 12.99. Found: C,
7.01; H, 1.02; N, 13.86. UV-vis (DCM) λmax nm (ε): 309
1
9. Mori, T.; Nishimura, T.; Yamamoto, T.; Doi, I.; Miyazaki, E.;
Osaka, I.; Takimiya, K. J. Am. Chem. Soc., 2013, 135,
1
3900-13913.
20. Mao, L.-K.; Hwang, J.-C.; Chueh, Y.-L. Org. Electron., 2014, 15,
2400-2407.
2
1. Oechsle, P.; Paradies, J. Org. Lett., 2014, 16, 4086-4089.
o
1
22. Takimiya, K.; Konda, Y.; Ebata, H.; Niihara, N.; Otsubo, T. J.
Org. Chem., 2005, 70, 10569-10571.
3
(
3
2
3. Okamoto, T.; Kudoh, K.; Wakamiya, A.; Yamaguchi, S. Org.
Chem., 2005, 7, 5301-5304.
+
24. Gabriel, S.; Leupold, E. Ber. Dtsch. Chem. Ges., 1898, 31,
159-1174.
24
8
4
1
6
(
2
2
2
5. Zheng, Y.; Miao, M.; Zhang, Y.; Nguyen, T.-Q.; Wudl, F. J. Am.
Chem. Soc., 2014, 136, 11614-11617.
6. Dou, L.; Zheng, Y.; Shen, X.; Wu, G.; Fields, K.; Hsu, W.-C.;
Zhou, H.; Yang, Y.; Wudl, F. Science, 2014, 343, 272-277.
7. Usta, H.; Risko, C.; Wang, Z.; Huang, H.; Deliomeroglu, M. K.;
Zhukhovitskiy, A.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc.,
296124), 354 (137502), and 541 (2994).
5
. Crystal Structures
Crystallographic data (excluding structure factors) for the
structures in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
numbers 1571470 and 1571471. The data can be obtained free of
charge via http://www.ccdc.cam.ac.uk or by e-mailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2
2
009, 131, 5586-5608.
28. Nielsen, C. B.; Voroshazi, E.; Holliday, S.; Cnops, K.; Rand, B.P.;
McCulloch, I. J. Mater. Chem. A, 2013, 1, 73-76.
9. Nishida, J.-I.; Deno, H.; Ichimura, S.; Nakagawa, T.; Yamashita,
Y. J. Mater. Chem., 2012, 22, 4483-4490.
0. Jacques, E.; Romain, M.; Yassin, A.; Bebiche, S.; Harnois, M.;
Mohammed-Brahim, T.; Rault-Berthelot, J.; Poriel, C. J. Mater.
Chem. C, 2014, 2, 3292-3302.
2
3
1
EZ, UK; fax: (+44) 1223/336-033, Tel.: (+44) 1223/336-408.
Acknowledges
This work was supported by the U.S. Department of
Energy, Office of Science, Basic Energy Sciences under
Award No. DESC-0012541. Y. Zheng acknowledges
financial support by the Wudl Chair, administered through
the Materials Department, School of Engineering, UCSB.
References and notes
1
.
Kaufman, J. H.; Chung, T.-C.; Heegar, A. J.; Wudl, F. J.
Electrochem. Soc., 1984, 131, 2092-2093.
2
3
4
5
6
.
Perepichka, I. F.; Perepichka, D. F.; Meng, H.; Wudl, F. Adv.
Mater., 2005, 17, 2281-2305.
Norsten, T. B.; Kantchev, E. A. B.; Sullivan, M. B. Org. Lett.,
.
2
010, 12, 4816-4819.
.
.
.
Siddesh, M. B.; Padmashali, B.; Thriveni, K. S.; Sandeep, C. J.
Chem. Sci., 2014, 126, 821-826.
Gramec, D.; Mašič, L. P.; Dolenc, M. S. Chem. Res. Toxicol.,
2
014, 27, 1344−1358.
Min, J.; Wang, P.; Srinivasan, S.; Nwachukwu, J. C.; Guo, P.;
Huang, M.; Carlson, K. E.; Katzenellenbogen, J. A.; Nettles, K.
W.; Zhou, H.-B. J. Med. Chem., 2013, 56, 3346-3366.
7
8
.
.
Triantou, D.; Soulis, S.; Koureli, S.; Sio, A. D.; Hauff, E. J. Appl.
Polym. Sci., 2013, 127, 585-592.
Chen, J.; Burrell, A.K.; Collis, G.E.; Officer, D.L.; Swiegers,
G.F.; Too, C.O.; Wallace, G.G. Electrochimica Acta., 2002, 47,
2
715-2724.
9
1
.
Rouhi, M.; Lakouraj, M. M.; Baghayeri, M.; Hasantabar, V. Int. J.
Polym. Mater., 2017, 66, 12-19.
0. Ortiz, R. P.; Herrera, H.; Blanco, R.; Huang, H.; Facchetti, A.;
Marks, T. J.; Zheng, Y.; Segura, J. L. J. Am. Chem. Soc., 2010,
1
32, 8440-8452.
1
1
1
1
1
1
1
1. Ito, H.; Yamamoto, T.; Yoshimoto, N.; Tsushima, N.; Muraoka,
H.; Ogawa, S. Heteroat. Chem., 2013, 24, 25-35.
2. Durban, M. M.; Kazarinoff, P. D.; Luscombe, C. K.
Macromolecules, 2010, 43, 6348-6352.
3. Murali, M. G.; Naveen, P.; Udayakumar, D.; Yadav, V.;
Srivastava, R. Tetrahedron Lett., 2012, 53, 157-161.
4. Turkoglu, G.; Cinar, M. E.; Buyruk, A.; Tekin, E.; Mucur, S. P.;
Kaya, K.; Ozturk, T. J. Mater. Chem. C., 2016, 4, 6045-6053.
5. Chen, C.-H.; Cheng, Y.-J.; Chang, C.-Y; Hsu, C.-S.
Macromolecules, 2011, 44, 8415-8424.
6. Park, Y. S.; Kale, T. S.; Nam, C.-Y.; Choi, D.; Grubbs, R. B.
Chem. Commun., 2014, 50, 7964-7967.
7. Kim, S.; Choi, H.; Baik, C.; Song, K.; Kang, S. O.; Ko, J.
Tetrahedron, 2007, 63, 11436-11443.