Isomeric indacenedibenzothiophenes: Synthesis, photoelectric properties and ambipolar semiconductivity

Article abstract of DOI:10.1039/c6tc01808d

A new strategy via double C-H activation cyclization has been developed for the versatile synthesis of IDBT derivatives with quite different photoelectric properties. Single-crystal field-effect transistors based on IDBT-l-TIPSA delivered high and balanced charge carrier mobilities of up to 0.64 cm² V^-1 s^-1 for holes and 0.34 cm² V^-1 s^-1 for electrons under ambient conditions.

Full text of DOI:10.1039/c6tc01808d

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Isomeric Indacenedibenzothiophenes: Synthesis, Photoelectric
Properties and Ambipolar Semiconductivity
Longbin Ren,ab Chunming Liu,ab Zhaohui Wanga and Xiaozhang Zhu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A new strategy via double C–H activation cyclization has been overcome these deficiencies because the extended π-
developed for the versatile synthesis of IDBT derivatives with conjugation can help induce intermolecular π–π stacking and a
quite different photoelectric properties. Single-crystal field-effect suitable HOMO energy level. Depending on the fusing
transistors based on IDBT-l-TIPS delivered high and balanced patterns, isomeric indenofluorenes may exhibit unique
charge carrier mobilities of up to 0.64 cm2 V–1 s–1 for holes and properties such as small-bandgap absorption9c and
0.34 cm2 V–1 s–1 for electrons under ambient conditions.
biradicaloid9f,g properties, but can only be prepared one at a
time. We report herein one-pot construction of two
isoelectronic IDBT cores with linear (IDBT-l) and angular (IDBT-
In organic electronics,1 ambipolar semiconductors2 are
essential for complementary metal-oxide semiconductor
(CMOS)-like integrated circuits and light-emitting transistors,3
which should simultaneously possess high HOMO (highest
occupied molecular orbital) and deep LUMO (lowest occupied
molecular orbital) energy levels to facilitate hole and electron
transport. Polyacenes,4 especially pentacene derivatives,5 are
classical p-type semiconductors. To date, N-heteropentacenes6
bearing deep LUMO energy levels have also been developed
for electron transport. By contrast, ambipolar polyacenes with
high and balanced hole/electron mobilities and, especially,
ambient stability are far from being achieved,7 which can be
ascribed to the dilemma of decreasing LUMO energy levels
with electron-withdrawing groups while keeping suitably high
HOMO energy levels. With inbuilt five-membered rings,8
indenofluorene derivatives9 without strong electron-
withdrawing substituents have recently been found to exhibit
intrinsically low LUMO energy levels and are expected to be
excellent candidates as ambipolar semiconductors.10 However,
the ambipolar feature of indenofluorenes is not fully explored,
i.e., 10–3 cm2 V–1 s–1 level in a single-crystal transistor11 and 10–
a
) configurations (Fig. 1) by double C-H activation. IDBT-l and
IDBT-a show different photoelectric properties. Compared
with IDBT-l’s, the first two excitation states of IDBT-a-Mes are
extremely weak, which results in short-wavelength absorption.
However, the electrochemical energy band gap of IDBT-a-Mes
is smaller than that of IDBT-l-Mes. By attaching weakly
electron-withdrawing triisopropylsilyl (TIPS) groups, IDBT-l-
TIPS shows significantly decreased electrochemical energy
band gap, 1.19 eV (IDBT-l-TIPS) vs 1.60 eV (IDBT-l-Mes),
optimal frontier orbital energies of –5.46 eV for HOMO and –
4.27 eV for LUMO and ordered intermolecular π–π stacking
with a short distance of 3.304 Å, which jointly are beneficial for
ambipolar carrier transport. Consequently, single-crystal field-
effect transistors (FETs) based on IDBT-l-TIPS can operate
under ambient conditions and exhibit high and balanced
charge carrier mobilities of up to 0.64 cm2 V–1 s–1 for holes and
0.34 cm2 V–1 s–1 for electrons, which is rare for conjugated
polycyclic hydrocarbons.
6
cm2 V–1 s–1 level in thin-film transistors,12 which can be
attributed to the unfavorable solid-state stacking and
improper HOMO/LUMO alignment. We think that the
indacenedibenzothiophene core (IDBT, Fig. 1)13 may possibly
Fig. 1 Isomeric indacenedibenzothiophenes.
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing,
The synthetic route toward IDBTs is shown in Scheme 1. The
100190, P. R. China
.
starting material
1 was prepared using a Stille-type cross-
b University of Chinese Academy of Sciences, Beijing 100049, P. R. China. *E-mail:
xzzhu@iccas.ac.cn
coupling reaction between benzo[b]thiophen-3-yltributylstan-
nane and terephthaloyl dichloride in 40% yield after
† Electronic Supplementary Informaꢀon (ESI) available: Synthesis, NMR Charts,
Crystal structure data, Device fabrication and characterization. See
DOI: 10.1039/x0xx00000x
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(a)
(b)
Fig. 2 Molecular structure (a, 50% probability ellipsoids) and packing (b) of IDBT-l-TIPS.
Bond lengths of s-indacene: C1–C2: 1.418 Å, C2–C3: 1.370 Å, C1i–C3: 1.445 Å, C1i–C12:
1.417 Å; C5–C12: 1.434 Å; C4–C5: 1.396 Å; C3–C4: 1.448 Å.
which indicates the stronger antiaromaticity of the former.
IDBT-l-TIPS crystals suitable for single-crystal X-ray analysis
were grown by slow diffusion of methanol into its di-
chloromethane solution.17 IDBT-l-TIPS shows a rigid and planar
IDBT framework (Fig. 2a) with a high C2h symmetry and sin-
gle/double-bond alternation because of the antiaromaticity.
The large IDBT-l core and TIPS pendants jointly facilitated one-
dimensional intermolecular π–π stacking with a short distance
of 3.304 Å, which is smaller than that of TIPS-pentacene, 3.349
Å, and a large overlap of the adjacent IDBT cores (center-to-
center distance: 8.05 Å), which is very favorable for charge
carrier transport (Fig. 2b). By contrast, IDBT-l-Mes bearing
bulky mesityl groups shows no intermolecular π−π stacking in
solid state,13 which may be the case for IDBT-a-Mes, but we
did not get its single crystals.
Scheme 1. Synthesis of indacenedibenzothiophenes. Reagents and conditions: (a)
Pd(OAc)2,
K2CO3,
AgOAc,
PivOH,
140
°C;
(b)
mesityllithium
or
((triisopropylsilyl)ethynyl)lithium, THF, –78 °C; (c) SnCl2, toluene, 40 °C.
recrystallization. Instead of the traditional method, i.e.,
intramolecular Friedel–Crafts acylation reaction under strong
acidic conditions, we selected a more succinct double C–H
activation reaction for the synthesis of diketone 2a. After
many attempts, we found that the double cyclization of
compound
1 can only proceed in pivalic acid (PivOH) because
the reaction under the reported conditions in trifluoroacetic
acid14 is quite inefficient, stopping at the monocyclization step.
Unexpectedly, angular analogue 2b was also obtained. Both
compounds 2a and 2b can hardly be dissolved in any solvent
and thus can be used for the next step without further
separation. IDBT-l-Mes and IDBT-a-Mes were synthesized
from a mixture of 2a and 2b and mesityllithium followed by
SnCl2 reduction as a blue and yellow solid, respectively. With a
similar procedure, IDBT-l-TIPS was smoothly synthesized from
compound 4a in 20% isolated yield as blue needle crystals
after recrystallization.15 By contrast, IDBT-a-TIPS is highly
unstable and cannot be separated.
The photophysical and electrochemical properties of IDBT
s
were examined in dichloromethane and are summarized in
Table 1. The isomeric IDBT-a-Mes and IDBT-l-Mes exhibit
disparate absorption spectra with longest absorptions at 472
nm (ε: 0.78
× × L
104 L mol–1 cm–1) and 618 nm (ε: 3.95 104
mol–1 cm–1) in dichloromethane, respectively (Fig. 3a), which
can be well explained by the theoretical calculations.
According to time-dependent density functional theory (TDDFT)
calculations at the B3LYP/TZP level (Fig. 4), we found that the
first excitation state of IDBT-l-Mes originated from the
HOMO–1 to LUMO transition (604 nm, f: 0.393). By contrast,
the first two excitation states of IDBT-a-Mes originating from
HOMO to LUMO (1133 nm, f: 0.008) and HOMO–1 to LUMO
(611 nm, f: 0.009) transitions are extremely weak and can
hardly be distinguished from its absorption spectrum. Only the
third excitation state of HOMO–2 to LUMO transition shows
reasonable oscillator strength, 470.2 nm (f: 0.36). IDBT-l-TIPS
with extended π conjugation exhibits further bathochromic
absorption at 682 nm with large absorption coefficient, (ε:
All three IDBT compounds were fully characterized by con-
ventional methods. IDBT-l-Mes shows the same NMR spectra
as those reported,13 with a single peak at δ 6.07 ppm assigned
to the two alkenyl hydrogens of the central quinoid ring. By
contrast, the corresponding alkenyl hydrogens in IDBT-a-Mes
are shifted upfield, δ 5.50 ppm, which indicates the enhanced
shielding effect from the two neighboring mesityl groups. By
contrast, the alkenyl hydrogens in IDBT-l-TIPS are shifted
downfield, δ 6.38 ppm, in the absence of mesityl groups. The
×
104 L mol–1 cm–1), which can be attributed to the HOMO
downfield-shift tendency from IDBT-a-Mes, IDBT-l-Mes to
7.68
IDBT-l-TIPS agrees well with the decreased antiaromaticities of
the quinoid rings from angular to linear IDBT cores, which are
–9.60 (IDBT-a-Mes), –12.14 (IDBT-l-Mes) and –11.64 ppm
to LUMO transition (708 nm, f: 0.51). Unlike angular-IDBT, the
HOMO and HOMO–1 orbitals of linear-IDBTs have very close
energy levels with small energy differences of 0.04 eV (IDBT-l-
Mes) and 0.11 eV (IDBT-l-TIPS), respectively. The HOMO–1 and
HOMO energy alignments of IDBT-l-Mes and IDBT-l-TIPS are
reversed with different substitutions, and thus the HOMO–1 of
IDBT-l-Mes and the HOMO of IDBT-l-TIPS show the same
orbital distribution. The cyclic voltammograms (CVs) of IDBT
are shown in Fig. 3b. All IDBT compounds have highly
(IDBT-l-TIPS) according to the nucleus-independent chemical
shift (NICS) calculations15 at the B3LYP/TZP level with the
Amsterdam Density Functional (ADF) program.16 The NICS
values of five-membered rings in IDBT-a-Mes and IDBT-l-Mes
are also quite different, –22.09 and –17.98 ppm, respectively,
2 | J. Name., 2012, 00, 1-3
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Table 1 Photophysical and electrochemical properties of IDBT-a-Mes, IDBT-l-Mes and
IDBT-l-TIPS.a
abs
λmax
1/2c
Ered
1/2c
Eox
ε
ε
Cpd.
ELUMO
EHOMO
(nm)
(V)
(V)
(eV)
(eV)
IDBT-a-Mes
IDBT-l-Mes
IDBT-l-TIPS
472
−1.31
(−1.40)d
−1.61d
0.30
0.40
0.50
−3.88
−3.79
−4.27
−5.30
−5.38
−5.46
(3.89)b
618
(4.60)b
Fig.
3
(a) UV–vis absorption spectra and (b) cyclic voltam-mograms of IDBTs in
photo of IDBT solutions, IDBT-a-Mes (left), IDBT-l-Mes
682
(4.89)b
−0.90
(−0.94)d
dichloromethane. Inset:
a
(middle) and IDBT-l-TIPS (right).
a Measured in dichloromethane. b Logarithmic values of absorption coefficients (L
mol–1 cm–1). c CV on a carbon electrode with n-Bu4NClO4 in dichloromethane (0.1
d
e
M, vs Fc+/Fc). The potential of the peak cathodic current. The LUMO/HOMO
energy levels were determined from ELUMO/HOMO = −(5.10 + Ered/oxonset).18
Fig. 4 DFT-calculated orbital energy diagram and pictorial representation of
frontier orbitals for IDBTs.
Fig. 5 (a) The micronanocrystal images of optical microscope and (b) FET device model
for the measurements of IDBT-l-TIPS. (c) TEM image of micronanocrystal from PVT
method with its matching to the SAED pattern. (d) XRD pattern of micronano-crystals.
(e) and (f) I–V transfer characteristics for hole and electron mobilities of the
representative IDBT-l-TIPS-based single-crystal FET devices.
amphoteric ability with at least one reversible or irreversible
oxidation and reduction process. IDBT-a-Mes can be oxidized
and reduced more easily than IDBT-l-Mes, 0.30 vs 0.40 V
(oxidation) and –1.40 vs –1.61 V (reduction), leading to a
smaller electrochemical band gap, 1.42 eV vs 1.60 eV. The
apparent inconsistency between electrochemical and optical
band gaps can be explained by the different nature of the first
thermal gold (Au) deposition, Au foils were pasted directly
onto the micronanocrystals as the source and drain electrodes,
which has been proved to be an efficient and convenient
method. The FET devices were fabricated along the growing
direction of micronanocrystals, and the method of FET
measurements is shown in Fig. 5b.19 Because of the LUMO
energy level below –4.0 eV,20 all of the FET measurements can
be performed under ambient conditions without any
protection. The transmission electron microscope (TEM)
patterns with the corresponding selected area electron
diffraction (SAED) of the single-crystal micronanocrystals are
seen as neat and smooth patterns in Fig. 5c, which suggests
that the carrier transporting direction in the a–b plane is
parallel to the substrate, while the X-ray diffraction (XRD)
image in Fig. 5d exhibits sharp and pure peaks, which indicates
that the d spacing is 10.95 Å between the adjacent layers. The
transistors exhibit a balanced ambipolar property with hole
mobilities of up to 0.64 cm2 V–1 s–1 (average value: 0.23 cm2 V–1
s–1 from 15 devices) and electron mobility up to 0.34 cm2 V–1 s–
excitation state. Compared with IDBT-l-Mes
, the redox
processes of IDBT-l-TIPS are negatively shifted by 0.20 V for
oxidation and significantly positively shifted by 0.67 V for
reduction, which results in appropriate HOMO (–5.46 eV) and
LUMO (–4.27 eV) energy levels for ambipolar carrier
transport.18 The HOMO/LUMO energy levels of IDBT-l-Mes are
quite close to those reported values. 13
Taking its optimized frontier orbital energies and
compacted π–π stacking into consideration, we selected IDBT-
l-TIPS to demonstrate the potential of IDBTs as ambipolar
semiconductors. IDBT-l-TIPS micronanocrystals were grown
using the physical vapor transport (PVT) method, which is
better than the solution-growing method because of the
absence of solvents. In the optical microscope (Fig. 5a), the
micronanocrystals on the modified substrate display as
smooth ribbons or sticks several dozens of micrometers in
length, which indicates the long range regularity of the array.
We prepared a series of micronanocrystal transistors with
doped n-type silicon wafer as the gate electrode and
octadecyltrichlorosilane-modified SiO2 as the dielectric layer
and selected the transistors with high quality single crystals
that are thin enough to ignore the resistance under measuring.
To avoid a negative effect from thermal radiation during
1
(average value: 0.15 cm2 V–1 s–1 from 14 devices). Typical
transfer characteristics are shown in Fig. 5e and 5f.
In summary, we have developed a new strategy, i.e., double
C–H activation cyclization, for the versatile synthesis of IDBT
derivatives, including isomeric IDBT-a and IDBT-l, which we
believe can be expanded for the preparation of various
indenofluorene analogues. Isomeric IDBT-l and IDBT-a have
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3733; (c) Y. Liu, C. Song, W. Zeng, K. Zhou, Z. Shi, C. Ma, F.
Yang, H. Zhang and X. Gong, J. Am. Chem. Soc. 2010, 132
16349; (d) Z. Liang, Q. Tang, R. Mao, D. Liu, J. Xu and Q.
Miao, Adv. Mater. 2011, 23, 5514; (e) A. R. Mohebbi, J. Yuen,
J. Fan, C. Munoz, M. F. Wang, R. S. Shirazi, J. Seifter and F.
Wudl, Adv. Mater. 2011, 23, 4644.
quite different photoelectric properties. Angular IDBT-a-Mes
shows shorter-wavelength absorption than linear IDBT-l-Mes
but with a narrower electrochemical energy band gap, the
origin of which has been elucidated by theoretical
,
investigations. Compared with IDBT-a-Mes and IDBT-l-Mes
,
8
(a) J. D. Wood, J. L. Jellison, A. D. Finke, L. Wang and K. N.
Plunkett, J. Am. Chem. Soc. 2012, 134, 15783; (b) A. R.
Mohebbi and F. Wudl, Chem.—Eur. J. 2011, 17, 2642; (c) J.
Shen, D. Yuan, Y. Qiao, X. Shen, Z. Zhang, Y. Zhong, Y. Yi and
X. Zhu, Org. Lett. 2014, 16, 4924; (d) C. Liu, S. Xu, W. Zhu, X.
IDBT-l-TIPS shows the most optimized HOMO/LUMO energy
levels of –5.46 eV for HOMO and –4.27 eV for LUMO and
ordered intermolecular π–π stacking with a short distance of
3.304 Å. Indeed, single-crystal FETs based on IDBT-l-TIPS
delivered high and balanced charge carrier mobilities of up to
0.64 cm2 V–1 s–1 for holes and 0.34 cm2 V–1 s–1 for electrons
under ambient conditions. Following the successful array of
the p-type TIPS-pentacene and n-type N-heteropentacenes,
nominally antiaromatic IDBT derivatives should function as
very promising candidates in the field of ambipolar carrier
transport and be worthy of intensive study.
Zhu, W. Hu, Z. Li and Z. Wang, Chem.—Eur. J. 2015, 21
,
17016–17022; (e) G. Dai, J. Chang, W. Zhang, S. Bai, K.-W.
Huang, J. Xu and C. Chi, Chem. Commun. 2015, 51, 503; (f) T.
Kawase, T. Fujiwara, C. Kitamura, A. Konishi, Y. Hirao, K.
Matsumoto, H. Kurata, T. Kubo, S. Shinamura, H. Mori, E.
Miyazaki and K. Takimiya, Angew. Chem., Int. Ed. 2010, 49
,
7728; (g) C. Lütke-Eversloh, Y. Avlasevich, C. Li and K. Müllen,
Chem.—Eur. J. 2011, 17, 12756.
9
(a) M. M. Haley, Chem. Rec. 2015, 15, 1140; (b) D. T. Chase,
B. D. Rose, S. P. McClintock, L. N. Zakharov and M. M. Haley,
Angew. Chem., Int. Ed. 2011, 50, 1127; (c) A. Shimizu and Y.
Tobe, Angew. Chem., Int. Ed. 2011, 50, 6906; (d) B. D. Rose,
D. T. Chase, C. D. Weber, L. N. Zakharov, M. C. Lonergan and
M. M. Haley, Org. Lett. 2011, 13, 2106; (e) D. T. Chase, A. G.
Fix, B. D. Rose, C. D. Weber, S. Nobusue, C. E. Stockwell, L. N.
Zakharov, M. C. Lonergan and M. M. Haley, Angew. Chem.,
Int. Ed. 2011, 50, 11103; (f) A. Shimizu, R. Kishi, M. Nakano,
D. Shiomi, K. Sato, T. Takui, I. Hisaki, M. Miyata and Y. Tobe,
Angew. Chem., Int. Ed. 2013, 52, 6076.
We thank the National Basic Research Program of China
(973 Program) (No. 2014CB643502), the Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDB12010200) and the National Natural Science Foundation
of China (91333113) for financial support. The authors are
grateful to Professor Shouke Yan of Beijing University of
Chemical Technology for help with the morphology simulation.
Notes and references
‡ The authors declare no competing financial interests.
10 (a) J. L. Marshall, M. M. Haley,Indenofluorenes and Related
Structures. In Organic Redox Systems: Synthesis, Properties,
and Applications; T. Nishinaga,, Ed.; John Wiley & Sons, Inc,
Hoboken, NJ, 2016; ch 10; (b) A. G. Fix, P. E. Deal, C. L.
Vonnegut, B. D. Rose, L. N. Zakharov and M. M. Haley, Org.
Lett. 2013, 15, 1362.
11 D. T. Chase, A. G. Fix, S. J. Kang, B. D. Rose, C. D. Weber, Y.
Zhong, L. N. Zakharov, M. C. Lonergan, C. Nuckolls and M. M.
Haley, J. Am. Chem. Soc. 2012, 134, 10349.
1
(a) A. J. Heeger, N. S. Sariciftci and E. B. Namdas,
Semiconducting and Metallic Polymers; Oxford University
Press: Oxford, 2010; (b) Hu, W.; Bai, F.; Gong, X.; Zhan, X.; Fu,
H.; Bjornholm, T. Organic Optoelectronics; Wiley: New York,
2012.
2
(a) K. Zhou, H. Dong, H. l. Zhang and W. Hu, Phys. Chem.
Chem. Phys. 2014, 16, 22448; (b) S. Z. Bisri, C. Piliego, J. Gao
and M. A. Loi, Adv. Mater. 2014, 26, 1176; (c) Y. Zhao, Y. Guo
and Y. Liu, Adv. Mater. 2013, 25, 5372; (d) M. Mas-Torrent
and C. Rovira, Chem. Soc. Rev. 2008, 37, 827; (e) J. Zaumseil
and H. Sirringhaus, Chem. Rev. 2007, 107, 1296.
12 J.-i. Nishida, S. Tsukaguchi and Y. Yamashita, Chem.—Eur. J.
2012, 18, 8964.
13 B. S. Young, D. T. Chase, J. L. Marshall, C. L. Vonnegut, L. N.
Zakharov and M. M. Haley, Chem. Sci. 2014, 5, 1008.
14 (a) H. Li, R.-Y. Zhu, W.-J. Shi, K.-H. He and Z.-J. Shi, Org. Lett.
2012, 14, 4850; (b) P. Gandeepan, C.-H. Hung and C.-H.
Cheng, Chem. Commun. 2012, 48, 9379.
15 P. von Ragué Schleyer, C. Maerker, A. Dransfeld, H. Jiao and
N. J. R. van Eikema Hommes, J. Am. Chem. Soc. 1996, 118,
6317.
16 G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C.
Fonseca Guerra, E. J. Baerends, J. G. Snijders and T. Ziegler, J.
Comput. Chem. 2001, 22, 931.
17 CCDC 1455199 contains the supplementary crystallographic
data for this paper. Thise data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
3
(a) E. J. Meijer, D. M. de Leeuw, S. Setayesh, E. van
Veenendaal, B.-H. Huisman, P. W. M. Blom, J. C. Hummelen,
U. Scherf and T. M. Klapwijk, Nature Mater. 2003, 2, 678; (b)
L. Bürgi, M. Turbiez, R. Pfeiffer, F. Bienewald, H.-J. Kirner and
C. Winnewisser, Adv. Mater. 2008, 20, 2217; (c) K.-J. Baeg, J.
Kim, D. Khim, M. Caironi, D.-Y. Kim, I.-K. You, J. R. Quinn, A.
Facchetti and Y.-Y. Noh, ACS Appl. Mater. Interfaces 2011,
3205; (d) K.-J. Baeg, D. Khim, S.-W. Jung, M. Kang, I.-K. You,
3,
D.-Y. Kim, A. Facchetti and Y.-Y. Noh, Adv. Mater. 2012, 24
5433.
,
4
5
(a) J. E. Anthony, Angew. Chem., Int. Ed. 2008, 47, 452; (b) J.
E. Anthony, Chem. Rev. 2006, 106, 5028; (c) L. Zhang, Y. Cao,
N. S. Colella, Y. Liang, J.-L. Brédas, K. N. Houk and A. L.
Briseno, J. Am. Chem. Soc. 2015, 136, 9248.
(a) J. E. Anthony, J. S. Brooks, D. L. Eaton and S. R. Parkin, J.
Am. Chem. Soc. 2001, 123, 9482; (b) Y. Diao, B. C.-K. Tee, G.
Giri, J. Xu, D. H. Kim, H. A. Becerril, R. M. Stoltenberg, T. H.
Lee, G. Xue, S. C. B. Mannsfeld and Z. Bao, Nature Mater.
2013, 12, 665.
18 C. M. Cardona, W. Li, A. E. Kaifer, D. Stockdale and G. C.
Bazan, Adv. Mater. 2011, 23, 2367.
19 (a) Q. Tang, Y. Tong, H. Li, Z. Ji, L. Li, W. Hu, Y. Liu and D. Zhu,
Adv. Mater. 2008, 20, 1511; (b) L. Tan, W. Jiang, L. Jiang, S.
Jiang, Z. Wang, S. Yan and W. Hu, Appl. Phys. Lett. 2009, 94
,
153306; (c) C. Liu,, C. Xiao Y. Li, W. Hu, Z. Li and Z. Wang,
Chem. Commun. 2014, 50, 12462.
6
7
(a) U. H. F. Bunz, J. U. Engelhart, B. D. Lindner and M.
Schaffroth, Angew. Chem., Int. Ed. 2013, 52, 3810; (b) Q.
Miao, Adv. Mater. 2014, 26, 5541.
(a) M. Tang, A. D. Reichardt, N. Miyaki, R. M. Stoltenberg and
Z. Bao, J. Am. Chem. Soc. 2008, 130, 6064; (b) M. Tang, J. H.
20 (a) H. Usta, C. Risko, Z. Wang, H. Huang, M. K. Deliomeroglu,
A. Zhukhovitskiy, A. Facchetti and T. J. Marks, J. Am. Chem.
Soc. 2009, 131, 5586; (b) Q. Ye, J. Chang, K.-W. Huang, X. Shi,
J. Wu and C. Chi, Org. Lett. 2013, 15, 1194.
Oh, A. D. Reichardt and Z. Bao, J. Am. Chem. Soc. 2009, 131
,
4 | J. Name., 2012, 00, 1-3
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Page 5 of 5
Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C6TC01808D
Isomeric Indacenedibenzothiophenes were synthesized by a new strategy via double C
−
H activation
cyclization and shows quite different and unique photoelectric properties. Single-crystal field-effect
transistors based on IDBT-l-TIPS delivered high and balanced charge carrier mobilities of up to 0.64 cm2 V–
1 s–1 for holes and 0.34 cm2 V–1 s–1 for electrons under ambient conditions.