Synthesis, photophysical properties, and field-effect characteristics of (ethynylphenyl)benzimidazole-decorated anthracene and perylene bisimide derivatives

Article abstract of DOI:10.1002/ejoc.201200032

A series of anthracene and perylene bisimide derivatives with electron-withdrawing benzimidazole substituents has been designed and prepared. Detailed studies on the electrochemical and photophysical properties as well as the field-effect mobilities of these new compounds were explored. The incorporation of electron-withdrawing benzimidazole groups lowered the LUMO levels in both anthracene and perylene bisimide derivatives compared to those of the parent compounds. Strong emission was observed for all anthracene derivatives, but only weak emission was observed for perylene bisimide derivatives. The anthracene derivatives showed typical p-type semiconducting character, even when the derivatives were substituted with electron-withdrawing benzimidazole groups at the 9- and 10-positions, which apparently does not lower the LUMO levels to transform them into electron-transporting molecules. Perylene bisimide derivatives displayed typical n-channel semiconducting properties with low threshold voltages and electron mobilities of ca. 5.2 × 10^-5 cm² V^-1 s^-1. Copyright

Full text of DOI:10.1002/ejoc.201200032

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FULL PAPER
DOI: 10.1002/ejoc.201200032
Synthesis, Photophysical Properties, and Field-Effect Characteristics of
(Ethynylphenyl)benzimidazole-Decorated Anthracene and Perylene Bisimide
Derivatives
I-Lin Lee,[a] Sie-Rong Li,[a] Kuan-Fu Chen,[a] Po-Jen Ku,[a] Ashutosh S. Singh,[a]
Hui-Tung Kuo,[a] Yuh-Sheng Wen,[a] Chi-Wei Chu,*[b] and Shih-Sheng Sun*[a]
Keywords: Polycycles / Arenes / Conjugation / Photophysics / Semiconductors
A series of anthracene and perylene bisimide derivatives
with electron-withdrawing benzimidazole substituents has
been designed and prepared. Detailed studies on the electro-
chemical and photophysical properties as well as the field-
effect mobilities of these new compounds were explored. The
incorporation of electron-withdrawing benzimidazole groups
lowered the LUMO levels in both anthracene and perylene
bisimide derivatives compared to those of the parent com-
pounds. Strong emission was observed for all anthracene de-
rivatives, but only weak emission was observed for perylene
bisimide derivatives. The anthracene derivatives showed
typical p-type semiconducting character, even when the de-
rivatives were substituted with electron-withdrawing benz-
imidazole groups at the 9- and 10-positions, which appar-
ently does not lower the LUMO levels to transform them into
electron-transporting molecules. Perylene bisimide deriva-
tives displayed typical n-channel semiconducting properties
with low threshold voltages and electron mobilities of ca.
5.2ϫ10–5 cm2 V–1 s–1
.
reasons for the relatively slow progress of n-type semicon-
ducting materials are that they are air- and/or moisture-
sensitive, they lack volatility for efficient film growth, and
they are somewhat difficult to synthesize.[5] Indeed, both
kinds of semiconductors are required for the fabrication of
complementary integrated circuits, bipolar transistors, or
organic p/n junctions. The development of new materials
with high electron affinities for n-channel semiconductors
has been an area of intensive research since the first report
of n-type OFETs based on metallophthalocyanines.[6] Many
electron-withdrawing substituents such as perfluoralkyl,[7]
perfluorophenyl,[8] imide,[9] cyano,[10] and fluoro[11] groups
have been incorporated into aromatic π-conjugated cores to
show desired n-type semiconducting properties.
Anthracene belongs to the class of acenes, but it is more
stable than larger acenes.[12] The derivatives of anthracene
have generally shown typical p-channel FET mobili-
ties.[12,13] The large π-conjugation in the anthracene core
has been proposed to enhance electron delocalization and
promote charge carrier mobility in the resulting FET de-
vices. On the other hand, perylene bisimide (PBI) deriva-
tives are promising candidates for applications in molecular
electronic devices.[14] A number of perylene bisimide deriva-
tives has shown impressive field-effect mobilities with n-
type semiconducting character due to the electron-deficient
nature of the perylene bisimide core.[2a,15] It is also possible
to convert typical electron-rich molecules to n-type semi-
conducting materials with appropriate incorporation of
Introduction
Great attention has been paid to developments in the
field of organic materials for field-effect transistors during
the past decade or two.[1] Such devices have potential appli-
cations in the switching element in flat panel displays and
smart cards. In general, organic field-effect transistors
(OFET) can be fabricated at low cost if they can be de-
posited from solution, as this enables the easy fabrication
over large areas and on flexible substrates.[2] Despite rapid
development in recent years, the quest for more effective
organic semiconductors that possess charge carrier mobili-
ties comparable to those of their inorganic counterparts still
requires more effort. In particular, p-type semiconducting
materials have shown great progress in recent years. Penta-
cene, for example, has shown one of the highest OFET mo-
bilities and nearly reached the intrinsic transport limit of
organic single crystals.[3] On the other hand, the develop-
ment of n-type OFETs has generally lagged behind p-type
OFETs, except for a few prominent examples.[4] The major
[a] Institute of Chemistry, Academia Sinica,
Taipei 115, Taiwan, ROC
Fax: +886-2-27831237
E-mail: sssun@chem.sinica.edu.tw
[b] Research Center for Applied Sciences, Academia Sinica,
Taipei 115, Taiwan, ROC
E-mail: gchu@gate.sinica.edu.tw
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200032.
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electron-withdrawing groups to lower the LUMO levels for mental analysis. They are highly thermally stable with de-
effective electron transport. It has been demonstrated that composition temperatures ranging from 247 °C (for 5) to
pentacene, as the benchmark p-channel compound, can be 464 °C (for 1) by thermogravimetric analysis accounting for
transformed into an n-type charge carrier by its substitution 5% mass loss as the thermolysis threshold. The high ther-
with electron-withdrawing groups.[11a] The principles of our mal stabilities of these compounds allow thin film prepara-
molecular design in the current study are based on (1) the tion over a broad range of annealing temperatures.
rigid core structures of anthracene and PBI with extended
Yellow single crystals of compound 1 were grown by slow
π-conjugation to facilitate efficient π-electron delocalization diffusion of hexane into a chloroform solution, and the
and possible intermolecular π–π stacking, (2) incorporation crystal structure determined by X-ray diffraction is shown
of electron-withdrawing benzimidazole segments to depress in Figure 1; the crystal and refinement parameters are col-
the LUMO levels for effective electron transport and air lected in Table S1 (Supporting Information). Compound 1
stability by energetically stabilizing the induced electrons crystallizes in the P21/c space group. The angle between the
during charge transport,[10c] and (3) alkyl side chains in the central anthracene and peripheral ethynylbenzaldehyde is
benzimidazole groups to increase solubility for easy solu- 19.2°. The molecules adopt herringbone packing in the
tion-processed fabrication without disrupting π-conjugation crystal, similar to that of anthracene.[1] There is no signifi-
in structural frameworks and to provide potential intrusion cant π–π overlap in the crystal structure, but there are
of oxygen and moisture into the active layer of the resulting strong C–H···π interactions between the anthracene and ad-
devices.[16] Herein, we report the synthesis, electrochemical, jacent benzaldehyde with a distance of 3.06 Å.
and photophysical properties and field-effect transistor
The electrochemical properties of anthracene and PBI
characteristics of a series of anthracene and PBI derivatives derivatives were characterized by cyclic voltammetry in
for n-type semiconductors by direct functionalization of the DMF or CH2Cl2 containing 0.1 m Bu4NPF6 as the support-
anthracene and PBI cores with electron-withdrawing (eth- ing electrolyte. Table 1 summarizes the potentials quoted
ynylphenyl)benzimidazole segments.
relative to the ferrocenium/ferrocene couple. The anthrac-
ene derivatives exhibit one or two reversible reduction
waves and one irreversible oxidation wave for bis[(ethynyl-
phenyl)benzimidazole] compounds 2–4, whereas no oxi-
dation wave could be observed for mono[(ethynylphenyl)-
benzimidazole] compounds 6 and 7 within the solvent win-
dow. Assuming that the Koopman’s theorem holds (EAred
≈ –LUMOred),[18] the LUMO levels can be estimated from
the first half-wave reduction potentials by taking the ferro-
Results and Discussion
Synthesis, Crystal Structure, and Electrochemical
Properties
The anthracene and perylene bisimide derivatives investi- cene energy level to be –4.8 eV below the vacuum level.[19]
gated in this work were synthesized according to the pro- The converted energy levels are also summarized in Table 1
cedures in Schemes 1 and 2, respectively. Anthracene deriv- for comparison. The LUMO levels in anthracene derivatives
atives 1–7 were obtained by palladium-catalyzed Sonoga- range from –2.96 to –3.49 eV, which are lower than the
shira coupling of 9-bromoanthracene or 9,10-dibromo- LUMO energy of parent 9,10-bis(phenylethynyl)anthracene
anthracene with the corresponding electron-withdrawing (εLUMO = –2.92 eV),[20] indicating that the electron-with-
(ethynylphenyl)benzimidazoles. The analytically pure prod- drawing effect of the aldehyde and benzimidazole groups
ucts were isolated by flash column chromatography.
played a part in lowering the LUMO energies. Indeed, the
The PBI derivatives were synthesized by direct function- LUMO energies of anthracene derivatives 1–7 are compar-
alization of the PBI core at the bay positions. We chose the able to some fluorinated or chlorinated anthracene deriva-
core PBI structure with branched alkyl chains attached to tives, indicating that the electronic effects of fluoride and
the imide nitrogen atoms to provide sufficient solubility for chloride substitution of the benzimidazole are similar.[21]
solution-processed semiconductors for OFETs. It is also
The first reduction potentials of the PBI derivatives
known that PBI derivatives bearing branched alkyl chains range from –0.83 V (for 10) to –1.01 V (for 11). PBI deriva-
are prone to organize into lamellar arrangements that are tives 9–12 can be easily reduced by ≈90–270 mV due to the
potentially advantageous for OFETs. Dibromoperylene bis- electron-withdrawing benzimidazole substituents when
imide derivative 8 was synthesized in two steps from per- compared to parent alkyl-substituted PBIs (Ered
=
ylene bis(anhydride) in a total yield of 69%. Subsequently, –1.10 V).[22] The LUMO levels of compounds 9–12 are
Sonogashira coupling of compound 8 with the correspond- comparable to some halo-substituted PBI deriva-
ing benzimidazole-derived phenyl acetylene afforded com- tives.[11a,11b,23] The benzimidazole substituents effectively
pounds 9, 11, and 12. Attempts to prepare 10 through di- lower the LUMO energy of 10 to –3.97 eV. The introduc-
rect palladium-catalyzed Sonogashira coupling of 8 with 2- tion of alkyl groups on the benzimidazoles not only signifi-
(4-ethynylphenyl)-1H-benzo[d]imidazole were unsuccess- cantly increases the solubility of compound 11 but also pro-
ful.[17] Instead, compound 10 was prepared by condensation vides hydrophobic side chains to prevent the intrusion of
reaction between 9 and o-phenylenediamine. All new com- oxygen and moisture into the active layer of the resulting
1
pounds synthesized were fully characterized by H NMR field-effect transistors. The drawback of these alkyl groups
spectroscopy, high-resolution mass spectrometry, and ele- is to slightly raise the LUMO energy up to –3.79 eV (for
2
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Photophysical Studies of Anthracene and Perylene Bisimide Derivatives
Scheme 1. Synthetic procedures for anthracene derivatives.
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Scheme 2. Synthetic procedures for perylene bisimide derivatives.
4
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Photophysical Studies of Anthracene and Perylene Bisimide Derivatives
Table 1. Redox potentials (vs. Fc/Fc+) and calculated HOMO and
LUMO energies.[a]
[c]
[c]
Compd.
Eox
Ered
εHOMO
εLUMO
[V]
[V]
[eV]
[eV]
1
0.77
0.54
0.68
0.72
–1.54, –1.72
–1.70
–5.57
–5.34
–5.48
–5.52
–3.25
–3.10
–2.98
–3.04
–2.96
–3.44
–3.49
–3.84
–3.97
–3.79
–3.86
2
3[b]
4[b]
5
–1.82
–1.76
–1.84
6
7
–1.36, –2.04
–1.30
–0.96, –1.16
–0.83, –1.08, –1.42
–1.01, –1.22
–0.94, –1.19
9[b]
10
11[b]
12[b]
[a] Measured in 0.1 m Bu4NPF6 in anhydrous DMF unless noted,
scan rate of 100 mVs–1, ferrocene served as internal standard.
[b] Measured in anhydrous CH2Cl2. [c] Determined according to
literature methods: εHOMO = –4.8 eV – Eox; εLUMO = –4.8 eV – Ered
.
Photophysical Properties
The absorption and fluorescence data of compounds 1–
12 are collected in Table 2. Representative absorption and
fluorescence spectra of compounds 3 and 11 are depicted
in Figure 2. The absorption spectra of anthracene deriva-
tives 1–7 show characteristic anthracene absorption features
between 400 and 500 nm.[20] The absorption maxima of the
bis[(ethynylphenyl)benzimidazole]-substituted compounds
are redshifted by ≈50–60 nm vs. the parent anthracene
and mono(ethynylphenyl)benzimidazole]-substituted com-
pounds. The bathochromic shift is consistent with enhanced
π-conjugation of the molecular backbone and the incorpo-
ration of the electron-withdrawing phenylbenzimidazole
Figure 1. Crystal structure of 1 (top) showing notable C–H···π
(middle) and π–π (bottom) interactions in the crystal packing.
11). This negative effect can be compensated by introducing group. Compounds 1–7 all exhibit strong fluorescence with
cyano groups in the benzimidazoles to bring the LUMO quantum yields higher than 0.5 and excited-state lifetimes
energy back down to –3.86 eV (for 12).
of a few nanoseconds.
Table 2. Absorption and fluorescence properties in DMF solution.
Compd.
Absorption
Fluorescence
λmax [nm] (εϫ10–3 [m–1 cm–1])
λfl [nm][a]
Φfl
τ [ns]
[a]
1
315 (18.2), 329 (24.8), 458 (32.4), 484 (34.3)
338 (14.5), 351 (14.3), 437 (sh., 10.0), 463 (13.9), 489 (13.5)
329 (38.0), 455 (38.3), 481 (40.1)
503
0.78
0.53
0.61
0.64
0.62
0.68
0.63
0.42
2.8
1.8
2.2
2.0
3.6
2.9
2.6
6.5
2
503
496
500
497
445
454
585
584
598
595
3
4
333 (40.3), 456 (39.3), 482 (41.3)
5
315 (13.7), 391 (14.0), 413 (23.3), 436 (22.8)
314 (8.5), 328 (13.2), 342 (14.3), 392 (9.4), 411 (14.8), 435 (13.9)
308 (22.3), 343 (21.9), 357 (25.3), 393 (20.6), 411 (32.5), 439 (31.0)
344, 358, 475, 523, 563
345 (48.2), 468 (14.4), 540 (15.8), 574 (15.6)
329 (57.4), 458 (12.7), 530 (20.1), 572 (25.1)
334 (65.7), 429 (15.2), 450 (14.0), 530 (24.8), 568 (35.4)
6
7
9
10
11
12
0.016
0.0077
0.057
1.3
[b]
5.8
[a] Fluorescence quantum yields in optically dilute toluene solution. The quantum yields were determined by using 9,10-diphenyl-
anthracene in cyclohexane (Φem = 0.90).[24] The molar absorptivity of compound 9 was not determined due to the extremely low solubility
in DMF. [b] The lifetime (Ͻ100 ps) is too short to be measured in our instrument.
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9 and is further redshifted to ≈570 nm for 10–12 due to the
extended conjugation on benzimidazoles. The HOMOs of
10 and 11 (Figure 3) calculated by using DFT with the
B3LYP/6-31+(d) basis set and the Gaussian03 program[26]
show electron delocalization to the (ethynylphenyl)benz-
imidazole moiety but only to the ethynylphenyl moiety in
the case of compound 12, whereas the LUMOs mainly con-
centrate in the parent PBI moiety with very minor extension
to the (ethynylphenyl)benzimidazole moieties.
The fluorescence maxima of compounds 9–12 all ap-
peared at λmax = 584–598 nm, which are mirror images rela-
tive to the respective S0–S1 absorption bands (see Figure 2).
Unlike typical PBI derivatives that usually display strong
fluorescence with quantum yields near unity, the PBI deriv-
atives of 10–12 showed very weak emission with emission
quantum yields lower than 0.06 and fluorescence lifetimes
on the nanosecond time scale. The lack of characteristic
vibrational features in the fluorescence spectra in com-
pounds 10–12 implies a less-rigid structural framework than
those of typical PBI derivatives that may contribute to a
more efficient nonradiative relaxation to give lower quan-
tum yields.
Figure 2. Absorption and fluorescence spectra of compounds 3
(dashed lines) and 11 (solid lines) measured in a DMF solution.
The absorption spectra of PBI derivatives 9–12 show typ-
ical spectral features of perylene bisimide chromophores in
the range of 450–600 nm with a well-defined vibronic struc-
ture.[25] As shown in Figure 2, a strong absorption band
near 330 nm is attributed to the π–π* transition located on
the (ethynylphenyl)benzimidazole moieties. The low solubil-
ity of compound 9 precluded a precise measurement of its
molar extinction coefficient in DMF. The absorption maxi-
mum of the allowed S0–S1 transition appears at 563 nm for
Thin-Film Transistor Device Characterization
The charge transport properties of these benzimidazole-
substituted anthracenes and perylene bisimides were exam-
ined through their incorporation into OFET devices.
OFETs with top-contact/bottom gate device structures were
fabricated by spin coating on octadecyltrichlorosilane
(OTS)-treated SiO2/p-type Si substrates. All spin-coating
processes were carried out under ambient conditions and
the devices were then annealed at 100 °C for 30 min under
an atmosphere of nitrogen. Finally, Ca/Al or Au contacts
were patterned by thermal evaporation by using a shadow
mask to give channel lengths of 100 μm and widths of
2 mm. FET properties were evaluated under positive or
negative gate bias under an atmosphere of nitrogen to ex-
plore the majority charge carrier type and device perform-
ance. All charge mobilities and threshold voltages were cal-
culated in the saturation regime. Table 3 summarizes the
FET data, and the representative transfer and output plots
for compound 11 are illustrated in Figure 4.
Table 3. Majority charge carrier types, field-effect mobilities (μ),
threshold voltages (VT), and current Ion/Ioff ratios for thin films of
compounds fabricated by spin-coating on OTS-treated SiO2/p+-Si
substrates.[a]
Compd. Polarity
μ [cm2 V–1 s–1]
Ion/Ioff
VT [V]
[b]
[b]
[b]
1
p
n
n
n
9
4.2ϫ10–6
5.2ϫ10–5
1.1ϫ10–5
10
10
9
12
6
11
12
102
[a] SiO2 dielectric (300 nm, Ci = 10 nF/cm2), L = 100 μm, W =
Figure 3. Pictorial presentation of the HOMOs and LUMOs of
compounds 11 (top) and 12 (bottom) calculated at the B3LYP/6-
31+(d) level solvated with THF.
2 mm. The mobilities were determined in the saturation regime
1/2
from the slope of plots of (IDS
small to extract the values.
)
vs. VGS. [b] The current is too
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Photophysical Studies of Anthracene and Perylene Bisimide Derivatives
strong diffractions in powder X-ray diffraction spectra of
compounds 9-, 11-, and 12-based thin films prepared from
spin-coating on Si/SiO2 with a nominal thickness of 50 nm
(see Figures S5–S7 in the Supporting Information).
Conclusions
In summary, we have prepared a series of potential n-
type semiconducting materials. The attachment of electron-
withdrawing benzimidazole groups to the parent
anthracene or perylene bisimide lowers the LUMOs of the
resulting compounds. Some of these benzimidazole-substi-
tuted perylene bisimides have measurable field-effect mo-
bilities. The anthracene derivative showed a typical charac-
ter of p-channel semiconducting properties, whereas per-
ylene bisimide derivatives displayed expected n-channel
semiconducting properties with electron mobilities of ca.
5.2ϫ10–5 cm2 V–1 s–1 and low threshold voltages. Relatively
easy synthetic accessibility and thermal stability of these
benzimidazole-substituted anthracenes and perylene bis-
imides allows for further functionalization to a variety of
new derivatives with potentials for understanding of charge
transport properties in these materials.
Experimental Section
Materials and Methods: All chemicals are commercially available
unless otherwise noted. All reactions and manipulations were car-
ried out under a nitrogen atmosphere with the use of standard in-
ert-atmosphere and Schlenk techniques. Solvents used for synthesis
were dried by standard procedures and stored under an atmosphere
of nitrogen. Compounds 8,[28] 2-(4-ethynylphenyl)benzimidazole,[29]
and 4,5-diaminophthalonitrile were synthesized according to pub-
lished methods. The syntheses of 1-dodecyl-2-(4-ethynylphenyl)-
benzimidazole and 1-dodecyl-2-(4-ethynylphenyl)benzimidazole-
5,6-dicarbonitrile are described in the Supporting Information.
NMR spectra were recorded with a Bruker AMX400 spectrometer.
Figure 4. Output characteristic (top) and I–V transfer plots (bot-
tom) for compound 11.
Devices fabricated with compounds 2–7 were found to
exhibit no FET activity. Compound 1 was found to show p-
channel character, whereas compounds 9, 11, and 12 exhibit
FET activity as n-channel semiconductors. Compound 10
was not fabricated for device measurement due to the ex-
tremely low solubility in common organic solvents. Com- 1H NMR chemical shifts are reported in ppm downfield from tet-
ramethylsilane (TMS) with the solvent resonances as internal stan-
dards. Cyclic voltammetry experiments were performed with a CHI
electrochemical analyzer. All measurements were carried out at
room temperature with a conventional three-electrode configura-
tion consisting of a platinum working electrode, a platinum wire
auxiliary electrode, and a nonaqueous Ag/AgNO3 reference elec-
trode.[30] The potentials were quoted against the ferrocene/ferrocen-
ium internal standard. The solvent containing 1.0 mm of the ana-
lyte and 0.1 m tetrabutylammonium hexafluorophosphate as the
supporting electrolyte in all experiments. Absorption spectra were
pound 1 is a p-channel semiconductor with very weak elec-
trical response. The attachment of electron-deficient benz-
imidazole groups is apparently not effective enough to
lower the LUMO level to allow the electron flow within the
device.
Compounds 9, 11, and 12 displayed n-channel properties
with a positive gate voltage bias to induce the accumulation
of electron carriers and current flows in the channel be-
tween source and drain electrodes. The highest mobility
among the three PBI derivatives was observed for com- obtained by using a Varian Cary 300 UV/Vis spectrophotometer.
Emission spectra were recorded with a Fluorolog III photolumines-
cence spectrometer. Luminescence quantum yields in solution were
calculated relative to diphenylanthracene in cyclohexane (Φ =
0.95).[24] Corrected emission spectra were used for the quantum
yield measurements and all reported data. Luminescence lifetimes
were determined on a time-correlated pulsed single-photon-count-
ing instrument as reported previously.[31] The geometry and elec-
tronic properties of the compounds were calculated with the
Gaussian03 program package.[26] All calculations were performed
by using density functional theory (DFT) with the B3LYP/6-
pound 11, which showed a charge carrier mobility of
5.2ϫ10–5 cm2 V–1 s–1. All three compounds gave excellent
threshold voltages with the values around 10 V or less. The
low VT indicates the carrier traps in the devices were rela-
tively few and resulted in such low threshold voltages. The
Ion/Ioff ratios, however, gave disappointing values of only
10–100. The low charge mobilities and Ion/Ioff ratios may
be attributed to the intrinsic molecular property or the lack
of long-range π stacking of the molecules in the thin film
morphology,[27] as implied from the lack of sharp and 31G+(d) basis set.
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Device Fabrication and Electrical Measurements: The devices were
fabricated on a heavily doped p-type Si wafer as gate electrode with
300-nm thick layer of thermally oxidized silicon dioxide. After rou-
tine solvent cleaning, the substrates were treated with octadecyl-
trichlorosilane following a procedure reported previously.[32] Then,
the semiconductor layer was spun over the (OTS)-treated SiO2 sur-
face from a 1 wt.-% ratio chloroform solution. Prior to source and
drain electrodes deposition, the device was thermally annealed on
a hot plate at 70 °C for a period of 30 min. Finally, layers of Ca
(30 nm) and Al (100 nm) were thermally evaporated under vacuum
(pressure: Ͻ6ϫ10–6 Torr) through a shadow mask to form the
source and drain electrodes. The typical channel length and width
of the devices were 100 and 2 mm, respectively. The electrical mea-
surements of the devices were performed by using a HP4156C semi-
conductor parameter analyzer. All the device fabrication and elec-
trical measurements were carried out in a nitrogen-filled glove box.
CDCl3): δ = 152.9, 143.1, 135.8, 132.2, 132.0, 130.8, 129.5, 127.2,
127.1, 124.8, 123.0, 122.6, 120.1, 118.5, 110.2, 102.0, 88.4, 44.9,
31.9, 29.8, 29.6, 29.5, 29.4, 29.3, 29.0, 26.7, 22.6, 14.1 ppm. HRMS
(FAB): calcd. for [M + H]+ 947.5992; found 947.5987.
Compound 4: A procedure similar to that outlined for the synthesis
of compound 3 was employed. The starting material was changed
from 1-dodecyl-2-(4-ethynylphenyl)benzimidazole to 1-dodecyl-2-
(4-ethynylphenyl)benzimidazole-5,6-dicarbonitrile. The desired
product was isolated as a bright orange solid (80 mg, 22%). 1H
NMR (400 MHz, CDCl3): δ = 8.72–8.69 (m, 4 H), 8.24 (s, 2 H),
7.99 (d, J = 7.6 Hz, 4 H), 7.86 (s, 2 H), 7.84 (d, J = 8.0 Hz, 4 H),
7.71–7.68 (m, 4 H), 4.35 (m, 4 H), 1.83 (m, 4 H), 1.26–1.17 (m, 36
H), 0.82 (t, J = 6.4 Hz, 6 H) ppm. 13C NMR was not acquired due
to low solubility. HRMS (FAB): calcd. for [M + H]+ 1047.5802;
found 1047.5807.
Compound 5: A procedure similar to that outlined for the synthesis
of compound 1 was employed. The starting material was changed
from 9,10-dibromoanthracene to 9-bromoanthracene. The desired
product was isolated as a golden yellow solid (0.85 g, 24%). M.p.
Compound 1: To a 150-mL flask containing 4-ethynylbenzaldehyde
(0.87 g, 6.7 mmol), 9,10-dibromoanthracene (1.1 g, 3.3 mmol),
Pd(PPh3)4 (0.38 g, 0.33 mmol), and CuI (62 mg, 0.33 mmol) was
added diisopropylamine (1 mL) and THF (60 mL). The resulting
mixture was heated at 80 °C under an atmosphere of nitrogen for
14 h before evaporating all volatiles under vacuum. The crude
product was purified by column chromatography (hexane/CH2Cl2,
1:5) and recrystallized (THF/EtOH) to afford compound 1 as a
1
136–139 °C. H NMR (300 MHz, CDCl3): δ = 10.1 (s, 2 H), 8.61
(d, J = 8.7 Hz, 2 H), 8.48 (s, 1 H), 8.03 (d, J = 8.4 Hz, 2 H), 7.93
(d, J = 8.4 Hz, 4 H), 7.62 (m, 2 H), 7.54 (m, 2 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 191.3, 135.4, 132.8, 131.9, 131.1, 129.8,
129.7, 128.8, 128.7, 126.9, 126.4, 125.8, 116.2, 99.8, 90.5 ppm.
HRMS (EI): calcd. for [M + Na]+ 306.1045; found 306.1049.
1
yellow solid (0.72 g, 51%). M.p. 224–226 °C. H NMR (400 MHz,
CDCl3): δ = 10.07 (s, 2 H), 8.65–8.69 (m, 4 H), 7.97 (d, J = 8.4 Hz,
2 H), 7.91 (d, J = 8.4 Hz, 2 H), 7.66–7.70 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 191.6, 136.0, 132.5, 132.4, 130.0, 129.7,
127.6, 127.4, 118.7, 102.0, 90.6 ppm. HRMS (EI): calcd. for [M]+
434.1307; found 434.1302. C32H18O2·0.2H2O (438.08): calcd. C
87.55, H 4.12; found C 87.55, H 4.25.
Compound 6: A procedure similar to that outlined for the synthesis
of compound 2 was employed. The starting material was changed
from 1 to 5. The desired product was isolated as a yellow solid
(45 mg, 64%). M.p. 180–184 °C. 1H NMR (400 MHz, [D6]acetone):
δ = 12.1 (s, 1 H), 8.74 (d, J = 8.8 Hz, 2 H), 8.68 (s, 1 H), 8.38 (d,
J = 8.0 Hz, 2 H), 8.18 (d, J = 8.4 Hz, 2 H), 8.03 (d, J = 8.4 Hz, 2
H), 7.70–7.74 (m, 3 H), 7.60–7.64 (m, 2 H), 7.56 (m, 1 H), 7.25 (m,
2 H) ppm. 13C NMR (100 MHz, [D6]acetone): δ = 151.7, 145.6,
136.3, 133.6, 133.1, 132.4, 131.7, 130.0, 129.4, 128.2, 127.8, 127.4,
127.0, 125.5, 124.0, 123.0, 120.5, 117.5, 112.2, 101.6, 88.7 ppm.
HRMS (APCI): calcd. for [M + H]+ 395.1548; found 395.1552.
Compound 2: To a 100-mL flask containing 1 (50 mg, 0.12 mmol),
o-phenylene diamine (27 mg, 0.25 mmol), and I2 (3 mg, 11.8 μmol)
was added THF/H2O (30:30 mL). The resulting mixture was stirred
in the dark for 3 d before evaporating all volatiles under vacuum.
The residue was extracted with CH2Cl2 and water. The organic
layer was collected, dried with MgSO4, and concentrated to dry-
ness. The crude solid was purified by column chromatography
(MeOH/CH2Cl2, 1:10). The obtained dark brown solid was further
sublimed at 330 °C to afford pure 2 as a brown solid (45 mg, 61%).
Compound 7: A procedure similar to that outlined for the synthesis
of compound 2 was employed. The starting materials were changed
from 1 and o-phenylene diamine to 5 and 4,5-diaminophthaloni-
trile. The desired product was isolated as a yellowish green solid
(70 mg, 49%). M.p. 176–178 °C. 1H NMR (400 MHz, [D6]DMSO):
δ = 14.2 (s, 1 H), 8.76 (s, 1 H), 8.65 (d, J = 8.8 Hz, 2 H), 8.55 (s,
1 H), 8.41–8.39 (m, 3 H), 8.21 (d, J = 8.4 Hz, 2 H), 8.12 (d, J =
8.0 Hz, 2 H), 7.77–7.74 (m, 2 H), 7.67–7.63 (m, 2 H) ppm. 13C
NMR (100 MHz, [D6]DMSO, 328 K): δ = 156.1, 132.0, 131.8,
130.5, 128.7, 128.5, 128.2, 127.5, 127.3, 125.8, 125.7, 125.2, 116.7,
115.2, 107.0, 100.0, 88.3 ppm. HRMS (FAB): calcd. for [M + H]+
445.1453; found 445.1456.
1
M.p. 261–264 °C. H NMR (400 MHz, [D6]DMSO): δ = 13.12 (s,
2 H), 8.76–8.78 (m, 4 H), 8.36 (d, J = 8.4 Hz, 4 H), 8.10 (d, J =
8.0 Hz, 4 H), 7.85–7.87 (m, 4 H), 7.65 (m, 4 H), 7.24–7.26 (m, 4
H) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 150.3, 143.9,
135.1, 132.2, 131.4, 130.6, 127.9, 126.8, 126.7, 123.2, 122.9, 121.9,
119.0, 117.6, 111.4, 102.7, 87.6 ppm. HRMS (ESI): calcd. for [M
+ H]+ 611.2236; found 611.2245.
Compound 3: To a 100-mL flask containing 1-dodecyl-2-(4-ethynyl-
phenyl)benzimidazole
(0.32 g,
0.83 mmol),
9,10-dibromo-
Compound 9: A procedure similar to that outlined for the synthesis
of compound 1 was employed. The starting material was changed
from 9,10-dibromoanthracene to compound 8. The desired product
was isolated as a dark purple solid (0.14 g, 41%). 1H NMR
(400 MHz, CDCl3): δ = 10.1 (s, 2 H), 9.98 (d, J = 8.0 Hz, 2 H),
8.87 (s, 2 H), 8.72 (d, J = 8.0 Hz, 2 H), 7.96 (d, J = 8.0 Hz, 4 H),
7.77 (d, J = 8.0 Hz, 4 H), 4.16 (m, 4 H), 2.00–1.96 (m, 4 H), 1.41–
1.23 (m, 14 H), 0.97–0.84 (m, 12 H) ppm. 13C NMR spectrum was
not acquired due to low solubility. HRMS (MALDI): calcd. for [M
+ H]+ 871.3747; found 871.3758.
anthracene (140 mg, 0.41 mmol), Pd(PPh3)4 (24 mg, 0.02 mmol),
and CuI (8 mg, 0.04 mmol) was added diisopropylamine (0.5 mL)
and THF (60 mL). The resulting mixture was heated at 80 °C under
an atmosphere of nitrogen for 24 h before evaporating all volatiles
under vacuum. The crude product was purified by column
chromatography (hexane, then hexane/CH2Cl2, 3:1). The obtained
solid was re-dissolved in a minimum amount of THF and precipi-
tated with EtOH (95%, 500 mL) to afford compound 3 as a yellow-
ish green solid (0.23 g, 59%). M.p. 115–118 °C. 1H NMR
(400 MHz, CDCl3): δ = 8.71–8.73 (m, 4 H), 7.93 (d, J = 8.0 Hz, 4
H), 7.82–7.84 (m, 6 H), 7.68 (br. s, 4 H), 7.43 (d, J = 5.0 Hz, 2 H), Compound 10: A procedure similar to that outlined for the synthe-
7.32–7.34 (m, 4 H), 4.28 (t, J = 7.2 Hz, 4 H), 1.85 (m, 4 H), 1.21–
sis of compound 2 was employed. The starting material was
changed from 1 to 8. After removal of all the volatiles under vac-
1.25 (m, 36 H), 0.82 (t, J = 6.0 Hz, 6 H) ppm. 13C NMR (100 MHz,
8
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20032
/KAP1
Date: 11-04-12 17:05:01
Pages: 11
Photophysical Studies of Anthracene and Perylene Bisimide Derivatives
Chem. 2011, 423–450; c) H. E. Katz, Z. Bao, S. L. Gilat, Acc.
Chem. Res. 2001, 34, 359–369.
a) J. E. Anthony, Chem. Rev. 2006, 106, 5028–5048; b) H.
Klauk, M. Halik, U. Zschieschang, G. Schmid, W. Radlik, J.
Appl. Phys. 2002, 92, 5259–5263.
uum, the residue was repeatedly washed with CH2Cl2 and ethyl
acetate to afford a dark purple solid (0.25 g, 69%). M.p. 232–
235 °C. The 1H NMR and 13C NMR spectra were not obtained
[3]
due to extremely low solubility. HRMS (MALDI): calcd. for [M +
H]+ 1047.4601; found 1047.4598.
[4]
F. Würthner, Angew. Chem. 2001, 113, 1069; Angew. Chem. Int.
Ed. 2001, 40, 1037–1039.
Compound 11: A procedure similar to that outlined for the synthe-
sis of compound 3 was employed. The starting material was
changed from 9,10-dibromoanthracene to compound 8. The de-
sired product was isolated as a dark purple solid (0.20 g, 44%).
M.p. 196–199 °C. 1H NMR (400 MHz, CDCl3): δ = 10.1 (d, J =
8.0 Hz, 2 H), 8.91 (s, 2 H), 8.76 (d, J = 8.4 Hz, 2 H), 7.78–7.86 (m,
10 H), 7.42 (m, 2 H), 7.32 (m, 2 H), 4.27 (t, J = 8.0 Hz, 4 H), 4.17
(m, 4 H), 1.85–1.97 (m, 8 H), 1.20–1.43 (m, 50 H), 0.96 (t, J =
7.2 Hz, 6 H), 0.89 (t, J = 6.0 Hz, 6 H), 0.80 (t, J = 6.8 Hz, 6
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 163.4, 163.0, 152.2,
143.0, 137.6, 135.9, 133.7, 133.4, 132.2, 131.8, 130.4, 129.9, 127.5,
127.3, 127.2, 123.4, 123.2, 123.1, 122.8, 122.1, 120.1, 119.8, 110.4,
98.6, 92.6, 45.1, 44.5, 38.1, 32.0, 31.0, 30.0, 29.8, 29.7, 29.6, 29.5,
29.3, 28.9, 26.9, 24.3, 23.2, 22.8, 14.3, 14.2, 10.8 ppm. HRMS
[5]
a) B. A. Jones, A. Facchetti, M. R. Wasielewski, T. J. Marks, J.
Am. Chem. Soc. 2007, 129, 15259–15278; b) B. A. Jones, A.
Facchetti, M. R. Wasielewski, T. J. Marks, Adv. Funct. Mater.
2008, 18, 1329–1339; c) R. T. Weitz, K. Amsharov, U. Zschies-
chang, E. B. Villas, D. K. Goswami, M. Burghard, H. Dosch,
M. Jansen, K. Kern, H. Klauk, J. Am. Chem. Soc. 2008, 130,
4637–4645.
a) G. Guillaud, M. Al Sadound, M. Maitrot, Chem. Phys. Lett.
1990, 167, 503–506; b) Z. Bao, A. Lovinger, J. Brown, J. Am.
Chem. Soc. 1998, 120, 207–208.
a) Y. Le, Y. Umemoto, M. Okabe, T. Kusunoki, K. I. Nakay-
ama, Y. J. Pu, J. Kido, H. Tada, Y. Aso, Org. Lett. 2008, 10,
833–836; b) S. Ando, J.-I. Nishida, E. Fujiwara, H. Tada, Y.
Inoue, S. Tokito, Y. Yamashita, Chem. Mater. 2005, 17, 1261–
1264; c) A. Facchetti, M. Mushrush, M. H. Yoon, G. R.
Hutchison, M. A. Ratner, T. J. Marks, J. Am. Chem. Soc. 2004,
126, 13859–13874.
a) J. A. Letizia, S. Cronin, R. P. Ortiz, A. Facchetti, M. A.
Ratner, T. J. Marks, Chem. Eur. J. 2010, 16, 1911–1928; b)
M. L. Tang, A. D. Reichardt, P. Wei, Z. Bao, J. Am. Chem.
Soc. 2009, 131, 5264–5273; c) C. R. Swartz, S. R. Parkin, J. E.
Bullock, J. E. Anthony, A. C. Mayer, G. G. Malliaras, Org.
Lett. 2005, 7, 3163–3166.
a) M. M. Durbant, P. D. Kazarinoff, Y. Segawa, C. K. Lus-
combe, Macromolecules 2011, 44, 4721–4728; b) Z. Wang, C.
Kim, A. Facchetti, T. J. Marks, J. Am. Chem. Soc. 2007, 129,
13362–13363.
a) S. Ando, A. Facchetti, T. J. Marks, Org. Lett. 2010, 12, 4852–
4855; b) H. Usta, C. Risko, Z. Wang, H. Huang, M. K. Deli-
omeroglu, A. Zhukhovitskiy, A. Facchetti, T. J. Marks, J. Am.
Chem. Soc. 2009, 131, 5586–5608; c) S. Handa, E. Miyazaki,
K. Takimiya, Y. Kunugi, J. Am. Chem. Soc. 2007, 129, 11684–
11685; d) C. R. Newman, C. D. Frisbie, D. A. da Silva Filho,
J.-L. Brédas, P. C. Ewbank, K. R. Mann, Chem. Mater. 2004,
16, 4436–4451.
a) F. Würthner, P. Osswald, R. Schmidt, T. E. Kaiser, H. Man-
sikkamäki, M. Könemann, Org. Lett. 2006, 8, 3765–3768; b)
Z. Chen, M. G. Debije, T. Debaerdemaeker, P. Osswald, F.
Würthner, ChemPhysChem 2004, 5, 137–140; c) Y. Sakamoto,
T. Suzuki, M. Kobayashi, Y. Gao, Y. Fukai, Y. Inoue, F. Sato,
J. Am. Chem. Soc. 2004, 126, 8138–8140.
a) A. R. Reddy, F. Fridman-Marueli, M. Bendikov, J. Org.
Chem. 2007, 72, 51–61; b) H. Meng, F. Sun, A. B. Goldfinger,
G. D. Jaycox, Z. Li, J. Marshall, G. S. Blackman, J. Am. Chem.
Soc. 2005, 127, 2406–2407; c) K. Ito, T. Suzuki, Y. Sakamoto,
D. Kubota, Y. Inoue, F. Sato, S. Tokito, Angew. Chem. 2003,
115, 1191; Angew. Chem. Int. Ed. 2003, 42, 1159–1162.
[6]
[7]
(FAB): calcd. for [M
C94H106N6O4·H2O (1401.90): C 80.53, H 7.76, N 5.99; found C
80.41, H 7.76, N 5.77.
+
H]+ 1383.8354; found 1383.8367.
[8]
Compound 12: A procedure similar to that outlined for the synthe-
sis of compound 4 was employed. The starting material was
changed from 9,10-dibromoanthracene to compound 8. The de-
sired product was isolated as a dark purple solid (30 mg, 39%).
M.p. 261–264 °C. 1H NMR (400 MHz, CDCl3): δ = 10.1 (d, J =
8.0 Hz, 2 H), 8.95 (s, 2 H), 8.78 (d, J = 8.4 Hz, 2 H), 8.24 (s, 2 H),
7.88 (s, 2 H), 7.86 (s, 4 H), 4.36 (t, J = 8.0 Hz, 4 H), 4.18 (m, 4 H),
1.86–1.97 (m, 8 H), 1.21–1.41 (m, 50 H), 0.96 (t, J = 7.2 Hz, 6 H),
0.89 (t, J = 7.2 Hz, 6 H), 0.80 (t, J = 6.4 Hz, 6 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 163.8, 163.4, 158.1, 145.3, 137.9, 134.6,
134.3, 132.7, 131.0, 130.0, 129.8, 128.2, 127.9, 126.8, 125.4, 123.6,
122.7, 119.8, 117.0, 116.6, 116.5, 109.5, 109.2, 97.1, 93.5, 46.1, 44.7,
38.3, 32.1, 31.1, 30.3, 29.8, 29.7, 29.6, 29.5, 29.2, 29.0, 26.9, 24.4,
23.3, 22.9, 14.3, 14.3, 10.9 ppm. HRMS (MALDI): calcd. for [M
+ H]+ 1484.9680; found 1484.8197.
[9]
[10]
CCDC-862005 (for 1) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
[11]
[12]
[13]
Supporting Information (see footnote on the first page of this arti-
cle): Synthetic procedures, HOMO and LUMO of compounds 9
and 10, output characteristic and I-V transfer plots for compounds
1
9 and 12, XRD spectra, H NMR and13C NMR spectra.
Acknowledgments
a) J. A. Hur, S. Y. Bae, K. H. Kim, T. W. Lee, M. J. Cho, D. H.
Choi, Org. Lett. 2011, 13, 1948–1951; b) F. Silvestri, A. Mar-
rocchi, M. Seri, C. Kim, T. J. Marks, A. Facchetti, A. Taticchi,
J. Am. Chem. Soc. 2010, 132, 6108–6123; c) A. Marrocchi, M.
Seri, C. Kim, A. Facchetti, A. Taticchi, T. J. Marks, Chem. Ma-
ter. 2009, 21, 2592–2594.
a) F. Würthner, Chem. Commun. 2004, 1564–1579; b) M. R.
Wasielewski, J. Org. Chem. 2006, 71, 5051–5066.
a) L. Perrin, P. Hudhomme, Eur. J. Org. Chem. 2011, 5427–
5440; b) R. Schmidt, J. H. Oh, Y.-S. Sun, M. Deppisch, A.-M.
Krause, K. Radacki, H. Braunschweig, M. Könemann, P. Erk,
Z. Bao, F. Würthner, J. Am. Chem. Soc. 2009, 131, 6215–6228.
We thank the National Science Council of Taiwan (grant No 100-
2628-M-001-002-MY3) and the Academia Sinica for support of
this research. S. R. L. thanks the National Science Council of Tai-
wan (grant No 100-2811-M-001-089) for a postdoctoral fellowship.
P. J. K. and H. T. K thank the Academia Sinica for postdoctoral
fellowships. Mass spectrometry analyses were performed at the
Mass Spectrometry Facility of the Institute of Chemistry, Acade-
mia Sinica.
[14]
[15]
[1] C. D. Dimitrakopoulos, P. R. L. Malenfant, Adv. Mater. 2002,
14, 99–117.
[16]
a) A. J. Jones, M. J. Ahrens, M.-H. Yoon, A. Facchetti, T. J.
Marks, M. R. Wasielewski, Angew. Chem. 2004, 116, 6523; An-
gew. Chem. Int. Ed. 2004, 43, 6363–6366; b) H. E. Katz, A. J.
[2] a) H. Usta, A. Facchetti, T. J. Marks, Acc. Chem. Res. 2011,
44, 501–510; b) A. Operamolla, G. M. Farinola, Eur. J. Org.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
9

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/KAP1
Date: 11-04-12 17:05:02
Pages: 11
C.-W. Chu, S.-S. Sun et al.
FULL PAPER
Lovinger, J. Johnson, C. Kloc, T. Slegrist, W. Li, Y.-Y. Lin, A.
Dodabalapur, Nature 2000, 404, 478–481.
[17] H. Weissman, E. Shirman, T. Ben-Moshe, R. Cohen, G. Leitus,
L. J. W. Shimon, B. Rybtchinski, Inorg. Chem. 2007, 46, 4790–
4792.
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R.
Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morok-
uma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzew-
ski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K.
Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V.
Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.
Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A.
Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Re-
vision C.02, Gaussian, Inc., Wallingford, CT, 2004.
[27] P. M. Beaujuge, J. M. J. Fréchet, J. Am. Chem. Soc. 2011, 133,
20009–20029.
[18] T. Koopmans, Physica 1934, 1, 104–113.
[19] I. Seguy, P. Jolinat, P. Destrule, R. Mamy, H. Allouchi, C. Co-
useille, M. Cotrait, H. Bock, ChemPhysChem 2001, 2, 448–452.
[20] a) J. C. Ribierre, A. Ruseckas, H. Cavaye, H. S. Barcena, P. L.
Burn, I. D. W. Samuel, J. Phys. Chem. A 2011, 115, 7401–7405;
b) C. Wang, Y. Liu, Z. Ji, E. Wang, R. Li, H. Jiang, Q. Tang,
H. Li, W. Hu, Chem. Mater. 2009, 21, 2840–2845.
[21] a) J. F. Tannaci, M. Noji, J. L. McBee, T. D. Tilley, J. Org.
Chem. 2008, 73, 7895–7900; b) J. F. Tannaci, M. Noji, J. L.
McBee, T. D. Tilley, J. Org. Chem. 2007, 72, 5567–5573.
[22] W. Qiu, S. Chen, X. Sun, Y. Liu, D. Zhu, Org. Lett. 2006, 8,
867–870.
[28] F. Würthner, V. Stepanenko, Z. Chen, C. R. Saha-Möller, N.
Kocher, D. Stalke, J. Org. Chem. 2004, 69, 7933–7939.
[29] L. Hu, M. L. Kully, D. W. Boykin, N. Abood, Bioorg. Med.
Chem. Lett. 2009, 19, 1292–1295.
[23] M. M. Ling, P. Erk, M. Gomez, M. Koenemann, J. Locklin,
Z. Bao, Adv. Mater. 2007, 19, 1123–1127.
[24] C.-Y. Hung, A. S. Singh, C.-W. Chen, Y.-S. Wen, S.-S. Sun,
Chem. Commun. 2009, 1511–1513.
[25] F. Würthner, Pure Appl. Chem. 2006, 78, 2341–2349.
[26] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T.
Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N.
Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P.
Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
[30] Y.-T. Shen, C.-H. Li, K.-C. Chang, S.-Y. Chin, H.-A. Lin, Y.-
M. Liu, C.-Y. Hung, H.-F. Hsu, S.-S. Sun, Langmuir 2009, 25,
8714–8722.
[31] a) K.-F. Chen, C.-W. Chang, J.-L. Lin, Y.-C. Hsu, M.-C. P. Yeh,
C.-P. Hsu, S.-S. Sun, Chem. Eur. J. 2010, 16, 12873–12882; b)
H.-C. Chen, C.-Y. Hung, K.-H. Wang, H.-L. Chen, W. S. Fann,
P. Chen, T. J. Chow, C.-P. Hsu, S.-S. Sun, Chem. Commun.
2009, 4064–4066; c) J.-L. Lin, C.-W. Chen, S.-S. Sun, A. J. Lees,
Chem. Commun. 2011, 47, 6030–6032.
[32] M. Shtein, J. Mapel, J. B. Benziger, S. R. Forrest, Appl. Phys.
Lett. 2002, 81, 268–270.
Received: January 11, 2012
Published Online: ᭿
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Job/Unit: O20032
/KAP1
Date: 11-04-12 17:05:02
Pages: 11
Photophysical Studies of Anthracene and Perylene Bisimide Derivatives
Optoelectronic Materials
The synthesis and photophysical studies of
a series of anthracene and perylene bis-
imide derivatives containing an electron-
I.-L. Lee, S.-R. Li, K.-F. Chen, P.-J. Ku,
A. S. Singh, H.-T. Kuo, Y.-S. Wen,
C.-W. Chu,* S.-S. Sun* ................... 1–11
deficient
(ethynylphenyl)benzimidazole
moiety are presented. Some of these mol-
ecules display n-channel semiconducting
properties.
Synthesis, Photophysical Properties, and
Field-Effect Characteristics of (Ethynyl-
phenyl)benzimidazole-Decorated Anthrac-
ene and Perylene Bisimide Derivatives
Keywords: Polycycles / Arenes / Conju-
gation / Photophysics / Semiconductors
Eur. J. Org. Chem. 0000, 0–0
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