Ambipolar transistor properties of 2,2′-binaphthosemiquinones

Article abstract of DOI:10.1039/c4tc02467b

Binaphthosemiquinones are proved to show ambipolar transistor properties. These compounds have characteristic blue colors owing to the small energy gaps, because the quinone part acts as an electron acceptor and the alkoxy group acts as an electron donor. Accordingly, these molecules have an analogous electronic structure to indigo. The crystal structure changes depending on the alkoxy groups, though these compounds generally have stacking structures.

Full text of DOI:10.1039/c4tc02467b

View Article Online
View Journal
Journal of
Materials Chemistry C
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: T. Higashino, S.
Kumeta, S. Tamura, Y. Ando, K. Ohmori, K. Suzuki and T. Mori, J. Mater. Chem. C, 2014, DOI:
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/materialsC

Page 1 of 8
Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C4TC02467B
Journal Name
RSCPublishing
ARTICLE
Ambipolar Transistor Properties of
2,2′ꢀBinaphthosemiquinones
Cite this: DOI:
10.1039/x0xx00000x
Toshiki Higashino,*a Shohei Kumeta,a Sumika Tamura,a Yoshio Ando,b Ken
Ohmori,b Keisuke Suzuki,b and Takehiko Mori*ac
Received 00th January 2012,
Accepted 00th January 2012
Binaphthosemiquinones are proved to show ambipolar transistor properties. These compounds
have characteristic blue colors owing to the small energy gaps, because the quinone part works
as an electron acceptor and the alkoxy group acts as an electron donor. Accordingly, these
molecules have an analogous electronic structure to indigo. The crystal structure changes
depending on the alkoxy groups, though these compounds generally have stacking structures.
DOI: 10.1039/x0xx00000x
www.rsc.org/
In general, aromatic compounds with a deep violet color are
candidates of ambipolar semiconductors. In this connection,
Introduction
In recent years, growing interests have been devoted to
ambipolar semiconductors because of the potential application
to largeꢀarea integrated circuits, lightꢀemitting transistors, and
photovoltaic devices.1 Among them, donorꢀacceptor (DꢀA)
copolymers composed of electronꢀrich and electronꢀdeficient
units have been investigated intensively owing to the high
performance and wellꢀbalanced ambipolar charge transport in
organic transistors.2 In particular, DꢀA copolymers composed
of diketopyrrolopyrrole (DPP) and thiophene derivatives
exhibit excellent ambipolar characteristics due to the
remarkable aggregation properties,3 where DPP works as the
acceptor part. As another acceptor unit, isoindigo has been
investigated recently,4 and indigo has been also used in an
ambipolar DꢀA copolymer.5 These ambipolar DꢀA copolymers
have a small band gap between the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital
(LUMO) levels, which is important for the effective hole and
electron injection from a single electrode material.
2,2′ꢀbinaphthosemiquinones (BNQs, Scheme 1) have
a
characteristic blue color, which has been known as Russing
blue for a long time.8 Since the NH moiety in indigo is an
electron donating group and has two π electrons, the C=C unit
with the alkoxy part in BNQ works analogously to the NH
group. Here we investigate electronic and crystal structures as
well as the transistor properties of BNQs with various alkyl
groups (Scheme 1).
Scheme 1. Synthesis of BNQ derivatives
It has been recently found, however, that the component
small molecule, indigo, exhibits ambipolar transistor
properties.6 In particular, dibromo and diphenyl indigo exhibit
much improved ambipolar transistor properties in the order of
0.1 ꢀ 1 cm2 V–1 s–1. This demonstrates that indigo itself is an
ambipolar material with a small HOMOꢀLUMO gap, and this is
quite convincing because the characteristic deep blue color with
the absorption edge around 720 nm is related to the small
HOMOꢀLUMO gap of 1.7 eV. The possibility of ambipolar
transport has been also suggested from the molecular orbital
calculation not only for indigo but also for isoindigo and DPP.7
Fig. 1 Molecular orbitals of 2a: (a) HOMO and (b) LUMO.
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 |
1

Journal of Materials Chemistry C
Page 2 of 8
ARTICLE
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C4TC02467B
Table 1 Redox potentials for BNQ derivatives (vs. Fc/Fc+ coupling = –4.80 eV).
EonsetOx (V)
0.48
EonsetRed (V)
–1.00
EHOMO (eV)
–5.28
ELUMO (eV)
–3.80
ꢀECV (eV)
1.48
ꢀEopt (eV)
1.75
2a
2b
2c
2e
2d
0.45
–1.01
–5.25
–3.79
1.46
1.73
0.42
–1.02
–5.22
–3.78
1.44
1.69
0.41
–1.03
–5.21
–3.77
1.44
1.68
0.47
–1.02
–5.27
–3.78
1.49
1.72
estimated as shown in Table 1. The HOMO level is about –5.3
eV and the LUMO level is –3.8 eV, and the resulting energy
gap is as narrow as 1.5 eV. This is attributed to the
semiquinone structure, suggesting the capability of these
compounds for both electron and hole transport. A general rule
has been suggested that hole transport is realized for Au
electrodes when the HOMO is located above –5.6 eV, and
electron transport is achieved when the LUMO level is located
deeper than –3.15 eV.10 The estimated HOMO/LUMO levels
of the present compounds satisfy these conditions.
These energy level values do not conflict with the results of
the density functional theory (DFT) calculations by Gaussian
09 program at the level of B3LYP using the 6ꢀ31G(d,p) basis
set (HOMO : –5.05 eV and LUMO : –2.89 eV for 2a).11 As
shown in Figure 1, the DFT calculation demonstrates
characteristic electron distribution of the HOMO and LUMO on
the semiquinone backbone; there is a large LUMO population
centered on the carbonyl carbons, whereas the HOMO
population is localized around the alkoxy carbons. Therefore,
naively speaking, the carbonyl groups act as the electron
Results and discussion
Synthesis
The synthesis of BNQ derivatives 2aꢀe is outlined in
Scheme 1. 1,4ꢀNaphthoquinone was reduced to 4ꢀalkoxyꢀ1ꢀ
naphthols 1aꢀe in the presence of the corresponding alcohols by
treatment with tin(II)chloride and concentrated hydrogen
chloride under reflux for 3 hours in 42ꢀ64% yields.9 The
obtained 4ꢀalkoxyꢀ1ꢀnaphthols 1aꢀe were oxidized with silver
(II)oxide in chloroform at room temperature for 3 hours to give
the corresponding BNQ derivatives 2aꢀe in 40ꢀ83% yields. All
BNQ derivatives are highly soluble in halogenated solvents,
and stable in the solid form.
Elecrtochemical properties
The electrochemical properties were studied by cyclic
voltammetry (Figure S1). All compounds showed two quasiꢀ
reversible reduction waves and one quasiꢀreversible oxidation
wave, from which the HOMO and LUMO energy levels were
Table 2 Crystallographic data for 2aꢀe.
Crystals
2a
2b
2c
2d
2e 13
Empirical formula
C22H16O4
344.37
Orthorhombic
P212121
4.5570(5)
18.571(2)
18.986(3)
90
C24H20O4
372.42
Monoclinic
P21/n
C26H24O4
400.47
Monoclinic
C2/c
C32H32O4
480.58
Monoclinic
C2/c
C32H36O4
484.61
Formula weight
Crystal system
Triclinic
Pꢀ1
Space group
a (Å)
12.2447(3)
4.98276(9)
15.1193(3)
90
29.3578(7)
4.3053(2)
18.6433(5)
90
23.0134(5)
16.3860(3)
15.4408(3)
90
5.3199(3)
10.5254(6)
12.2657(9)
71.587(6)
82.118(5)
75.890(5)
630.63(7)
1
b (Å)
c (Å)
α (°)
β (°)
90
93.255(1)
90
118.437(2)
90
119.5322(9)
90
γ (°)
V (Å3)
90
1606.8(3)
4
920.97(3)
2
2072.1(1)
4
5066.2(2)
8
Z
Unique reflns. (Rint)
Dcal (g/cm3)
2948 (0.0933)
1.423
1664 (0.1752)
1.343
1866 (0.0357)
1.284
4599 (0.0311)
1.255
2346 (0.0369)
1.276
R1
0.0859
0.1917
1.089
0.0638
0.1527
1.012
0.0413
0.0904
1.024
0.0419
0.1020
1.240
0.0414
Rw
0.1138
GOF
0.964
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 8
Journal Name
Journal of Materials Chemistry C
View Article Online
ARTICLE
DOI: 10.1039/C4TC02467B
Fig. 2 Crystal structures of 2a, viewed along (a) the stacking direction
and (b) the molecular short axis, and (c) the overlap modes.
Fig. 4 Crystal structures of 2c, viewed along (a) the stacking direction
and (b) the molecular short axis, and (c) the overlap modes.
Fig. 3 Crystal structures of 2b, viewed along (a) the stacking direction
Fig. 5 Crystal structures of 2d, viewed along (a) the stacking direction
and (b) the molecular short axis, and (c) the overlap modes.
and (b) the molecular short axis, and (c) the overlap modes.
acceptors and the alkoxy groups as the electron donors. This is screw axes, the long axes of the molecules in the adjacent
analogous to indigo having the large LUMO population on the stacks are not parallel, and oriented alternately.
carbonyl groups, and the HOMO population on the amino
groups.12
A crystal of 2b belongs to a monoclinic system with the
space group 21/ , where the crystal packing is depicted in
P
n
Figure 3. The crystallographically independent unit consists of
half the molecule, and the unit cell contains two molecules.
The molecule is almost planar, and forms a oneꢀdimensional
Crystal structures
Needleꢀlike black crystals of the BNQ derivatives 2aꢀe were
obtained by recrystallization from toluene. Single crystal Xꢀray
uniform stack along the
b axis. All molecular long axes are
oriented parallel in the ac plane, but tilted alternately, so that
when viewed from the molecular short axis, the structure looks
like the herringbone structure (Fig. 3(b)).
structure analyses were carried out for 2a
Table 1 shows the crystallographic data together with the
reported data of 2e 13
These compounds have respectively
different crystal structures.
A crystal of 2a belongs to an orthorhombic system with the
space group 212121. The crystal packing is depicted in Figure
, 2b, 2c, and 2d.
.
A crystal of 2c belongs to the space group
C2/c, where the
crystal packing is depicted in Figure 4. Half the molecule is
crystallographically independent, and a unit cell contains four
molecules. Similarly to 2b, the planar molecules form a oneꢀ
P
2. One molecule is crystallographically independent, and the
unit cell contains four molecules, which are related to each
other by a 21ꢀscrew axis running along the three different
crystallographic axes. The molecule is almost planar, and
dimensional uniform stack along the
view from the molecular short axis looks like the herringboneꢀ
like packing as well.
bꢀaxis, where the side
A crystal of 2d belongs to a monoclinic system with the
forms a oneꢀdimensional uniform stack along the
aꢀaxis with
space group
C2/c, where the crystal packing is depicted in
the interplanar spacing of 3.36 (Table 3). On account of the
Å
Figure 5. The unit cell contains eight molecules, and one
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 |
3

Journal of Materials Chemistry C
Page 4 of 8
VJieowuArrtnicalelONnlainme e
ARTICLE
DOI: 10.1039/C4TC02467B
using two carbonyl O atoms and two alkoxy O atoms (O···C:
3.44 Å), which indicates the relatively dense packing of 2b 7a,15
The present BNQ compounds (2a ) are entirely planar due
Table 3 Transfer integrals and geometries of 2aꢀe.
.
ꢀ
c
to the central C=C double bond. On the other hand, the
corresponding oxidized quinone, 2,2′ꢀbiꢀ1,4ꢀnaphthoquinone,
has a twisted structure; at the central C2ꢀC2′ single bond the
aromatic planes are twisted with the torsion angle of 47.3°.16
The resulting intramolecular O···H distance is 2.54 Å, which is
considerably longer than 2.05 Å in the present compounds.
tHOMO
(meV)
tLUMO
(meV)
x
(Å)
y
(Å)
z
(Å)
mode
Overlap modes and transfer integrals
2a
2b
2c
a
–59
–58
11
–35
51
3.06
3.66
2.27
0.52
3.78
4.03
0.36
0.68
0.89
0.19
0.75
0.94
3.36
3.32
3.55
3.37
3.63
3.34
In order to compare the intermolecular interaction more
carefully, the geometries of the BNQ molecules in the stack are
compared in Table 3 together with the intermolecular HOMOꢀ
HOMO and LUMOꢀLUMO transfer integrals. The respective
overlap modes are depicted in Figure 2(c), 3(c), 4(c), and 5(c).
Here, the direction of the central C=C double bond is defined as
b
b
–54
30
c1
c2
a
27
2d
2e
8
–46
87
the
plane is taken as the
molecule in the stack is represented by the (
Accordingly, the component means the interplanar distance.
In 2a and 2b, the displacement is comparatively small (
0.7 Å), and the stacked molecules are slipped mainly along the
axis, namely parallel to the central C=C bond. Since the
x
axis (Table 3), and its vertical direction in the molecular
axis. Then the position of the adjacent
) coordinates.
–32
y
x, y, z
molecule is crystallographically independent. The molecule is
not perfectly planar, and the two naphthyl parts make an angle
of 14.2° due to the large steric hindrance of the cyclohexyl
groups. The molecules are dimerized along the cꢀaxis stack,
forming a oneꢀdimensional column with two kinds of πꢀπ
overlaps,
z
y
y <
x
x
displacement is around 3.0 ~ 3.7 Å, the stacking mode looks
like a ringꢀoverꢀbond type (Figure 2(c) and 3(c)). These
In contrast to indigo, BNQ does not form strong
intercolumnar N–H···O hydrogen bonds because the donor part
is replaced by an alkoxy group; this is probably associated with
the thin needleꢀlike shape of the BNQ crystals. However, there
are many intermolecular C–H···O hydrogen bonds using alkyl
and aromatic hydrogens, where the typical distance from the
carbonyl O to the alkyl C is 3.18 ~ 3.43 Å.14 Compound 2a has
an additional hydrogen bond using the alkoxy O···C, 3.56 Å.
Compound 2b is stabilized by the hydrogen bond network
compounds have short interplanar distances (z displacement) of
3.36 Å and 3.32 Å, and comparatively large transfer integrals.
By contrast, 2c has a nearly eclipsed stacking mode (Figure
4(c)), and as a result, the interplanar distance is slightly large
(3.55 Å). Compound 2d has a dimerized structure, where the
geometry c2 is not much different from those of 2a and 2b
,
though the interplanar distance is somewhat large (3.63 Å). In
c1, the molecular long axes are no more parallel but connected
Fig. 6 Characteristics of the ambipolar transistors based on 2b deposited on TTC. (a) Transfer characteristics in the pꢀchannel region, and (b) the nꢀ
channel region. (c) Output characteristics in the pꢀchannel region, and (d) the nꢀchannel region.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 8
Journal Name
Journal of Materials Chemistry C
View Article Online
ARTICLE
DOI: 10.1039/C4TC02467B
of these compounds were investigated, but not successfully
operated.
The transfer and output characteristics of the 2b device are
shown in Figure 6, and the extracted parameters are listed in
Table 4 Transistor characteristics for 2aꢀc.
ꢁave [ꢁmax] (cm2 V–1 s–1)
8.2 × 10–4 [1.8 × 10–3]
7.0 × 10–4 [1.2 × 10–3]
1.3 × 10–3 [3.6 × 10–3]
4.7 × 10–3 [6.2 × 10–3]
5.7 × 10–4 [1.1 × 10–3]
1.2 × 10–4 [2.5 × 10–4]
Vthave (V)
on/offave
4 × 104
4 × 103
1 × 104
1 × 104
5 × 103
1 × 103
h
e
h
e
h
e
–1.5
29
2a
2b
2c
Table 4 together with the results of 2a and 2c. The device
exhibits typical ambipolar behavior; it can be operated both at
negative and positive gate voltages (VG). The hole and electron
transporting properties are well balanced, with the hole and
electron average mobilities around 1.3 × 10–3 cm2 V–1 s–1 and
4.7 × 10–3 cm2 V–1 s–1, respectively. The balanced performance
does not conflict with the balanced transfer integrals estimated
from the crystal packing (Table 3). Although the mobility
values are moderate, we have achieved large on/off ratios
exceeding 104 (Table 4). In addition, the ambipolar regions are
clearly observed in the output characteristics (Figures 6(c) and
(d)). This is represented by the comparatively small threshold
voltages Vth (Table 4). The threshold voltages are also
estimated from the rise of the reversed current in the output
–0.1
10
–2
30
by a twoꢀfold axis (Figure 5(c)), where the small
displacements imply that the molecular center is placed
approximately on the top of the other molecule. The
considerable dimerization is also obvious from the calculated
transfer integrals. The geometry of 2e is in principle not much
x and y
characteristics according to VT' = VG
– VD, which are in good
different from those of 2a and 2b, though the
x and y
agreement with the estimations from the transfer
characteristics.6d,17 The transistor of 2b shows ambipolar
performance even under ambient conditions and after severalꢀ
months storage under air (Figure S3). Compounds 2a and 2c
show slightly smaller mobilities, and the hole transport is larger
than the electron transport (Figure S4 and S5); the hole current
is obviously by one order of magnitude larger than the electron
current. In view of the energy levels (Table 1), the hole
transport is to some extent preferable to the electron transport in
displacements are somewhat enlarged. There is a general
tendency that large alkyl groups reduce the intermolecular
overlap. The large transfer integrals are observed only in the
stacking direction, and there are no meaningful intercolumnar
transfer integrals.
These compounds have highly oneꢀ
dimensional electronic structures, though the resulting
bandwidths are not very small (~0.2 eV). The signs of the
transfer integrals change depending on the compounds (Table
3), because the intermolecular overlap modes are respectively
different.
these materials. The decreasing order of mobility 2b
> 2a > 2c
roughly coincides with the increasing order of the interplanar
distances (Table 3), and the mobility is related to the preferable
molecular packing. However, the generally small mobility is
ascribable to the oneꢀdimensional structure, where the charge
transport is restricted in the stacking direction.
Transistor properties
In order to investigate chargeꢀcarrier transport in BNQ
derivatives, the organic thinꢀfilm transistors were fabricated.
Tetratetracontane (C44H90, TTC) was evaporated on the
thermally grown silicon oxide layer of an nꢀtype silicon wafer.
TTC is a highly hydrophobic material with a small dielectric
constant, and recently proved to be an excellent passivation
layer to observe ambipolar transport.6 Compounds 2a
2c were vacuum evaporated. Then, gold sourceꢀdrain
electrodes were evaporated on the active layer, and the resulting
bottomꢀgate topꢀcontact devices were investigated under
Thin film properties
Figure 7 shows the Xꢀray diffraction (XRD) patterns and
the AFM topographical images.
AFM images show
,
2b, and
polycrystalline thin films composed of needleꢀlike grains of
several micrometers, indicating the oneꢀdimensional pathway
along the elongated axis. The XRD patterns show a broad peak
centered at about 4.4° (
dꢀspacing = 20 Å) corresponding to the
vacuum and ambient conditions.
evaporated films of 2d and 2e. Transistors of spinꢀcoated films
We could not obtain
(006) reflection of the orientated TTC film.18 The primary thinꢀ
Fig. 7 Xꢀray diffraction patterns and AFM topographical images of 40 nm BNQ thinꢀfilms deposited on TTC: (a) 2a, (b) 2b, and (c) 2c.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 |
5

Journal of Materials Chemistry C
Page 6 of 8
VJieowuArrtnicalelONnlainme e
ARTICLE
DOI: 10.1039/C4TC02467B
film
for 2b, and 12.7 Å for 2c
correspond to /2, ( )/2, and (
d
ꢀspacings of 2a
ꢀ
c
are estimated to be 9.2 Å for 2a, 9.5 Å
These ꢀspacings respectively
sin )/2 of the crystal lattice,
1
(a) M. Muccini, Nat. Mater., 2006, 5, 605; (b) J. Zaumseil
and H. Sirringhaus, Chem. Rev., 2007, 107, 1296; (c) F.
Cicoira and C. Santato, Adv. Funct. Mater., 2007, 17, 3421;
.
d
β
b
a
–
c
a
indicating that the alkyl chains are standing perpendicular to the
substrate for 2b and 2c with keeping the molecular layers
parallel to the substrate. From this, the molecular planes are
tilted from the substrate normal by 13° for 2a, 5° for 2b, and
18° for 2c. The molecules of 2b are aligned most closely to the
vertical direction of the substrate. It has been demonstrated that
the charge mobility is maximized when the molecules are
exactly perpendicular to the substrate, and decreases as the tilt
angle increases.19 This rule is valid in the present compounds.
(d) K.ꢀJ. Baeg , M. Caironi and Y.ꢀY. Noh, Adv. Mater.
2013, 25, 4210. (e) S. Hotta, T. Yamao, S. Z. Bisri, T.
Takenobu and Y. Iwasa, J. Mater. Chem. C, 2014, , 965;
(f) Y. Wakayama, R. Hayakawa and H.ꢀS. Seo, Sci.
Technol. Adv. Mater., 2014, 15, 024202.
(a) J. D. Yuen, R. Kumar, D. Zakhidov, J. Seifter, B. Lim,
A. J. Heeger and F. Wudl, Adv. Mater., 2011, 23, 3780; (b)
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.
,
2
2
Mater. Inter., 2011, 3, 3205; (c) J. Fan, J. D. Yuen, M.
Wang, J. Seifter, J.ꢀH. Seo, A. R. Mohebbi, D. Zakhidov,
A. Heeger and F. Wudl, Adv. Mater., 2012, 24, 2186; (d) H.
Conclusions
Binaphthosemiquinones are proved to show ambipolar
transistor properties. These compounds have oneꢀdimensional
stacks, and because the charge transport is restricted in the
stacking direction, the hole and electron mobilities are in the
order of 10–3 cm2 V–1 s–1. In general, there is a tendency that a
bulky alkyl group reduces the intermolecular overlap and
charge transport properties. The ambipolar properties are
obviously associated with the small HOMOꢀLUMO gaps and
the characteristic blue colors. Such a property comes from the
semiquinone structure. The quinone parts work as an electron
acceptor and the alkoxy groups act as an electron donor, and
these molecules contain donor and acceptor parts in a molecule.
The present work demonstrates retrospectively that indigo is, in
a sense, regarded as a modified semiquinone. These molecules
are certainly of interest as a component of organic electronic
materials such as donorꢀacceptor polymers, but it is also of
interest how a small HOMOꢀLUMO gap is realized in a small
molecule with a minimal structure.
Usta, C. Newman, Z. Chen and A. Facchetti, Adv. Mater.
,
2012, 24, 3678; (e) K.ꢀJ. Baeg, D. Khim, S.ꢀW. Jung, M.
Kang, I.ꢀK. You, D.ꢀY. Kim, A. Facchetti and Y.ꢀY. Noh,
Adv. Mater., 2012, 24, 5433; (f) J. Kim, K.ꢀJ. Baeg, D.
Khim, D. T. James, J.ꢀS. Kim, B. Lim, J.ꢀM. Yun, H.ꢀG.
Jeong, P. S. K. Amegadze, Y.ꢀY. Noh and D.ꢀY. Kim,
Chem. Mater., 2013, 25, 1572; (g) T. Lei, J.ꢀH. Dou, X.ꢀY.
Cao, J.ꢀY. Wang and J. Pei, Adv. Mater., 2013, 25, 6589;
(h) J. W. Rumer, M. Levick, S.ꢀY. Dai, S. Rossbauer, Z.
Huang, L. Biniek, T. D. Anthopoulos, J. R. Durrant, D. J.
Procterb and I. McCullocha, Chem. Commun., 2013, 49
4465; (i) H. Chen, Y. Guo, Z. Mao, G. Yu, J. Huang, Y.
Zhao and Y. Liu, Chem. Mater., 2013, 25, 3589; (j) C. Guo,
B. Sun, J. Quinn, Z. Yan and Y. Li, J. Mater. Chem. C
,
,
2014, , 4289, (k) T. T. Steckler, P. Henriksson, S.
2
Mollinger, A. Lundin, A. Salleo and M. R. Andersson, J.
Am. Chem. Soc., 2014, 136, 1190.
(a) J. D. Yuen, J. Fan, J. Seifter, B. Lim, R. Hufschmid, A.
3
J. Heeger and F. Wudl, J. Am. Chem. Soc., 2011, 133
,
Acknowledgements
20799; (b) J. Lee, A.ꢀR. Han, J. Kim, Y. Kim, J. H. Oh and
C. Yang, J. Am. Chem. Soc., 2012, 134, 20713; (c) T.ꢀJ. Ha,
P. Sonar, S. P. Singh and A. Dodabalapur, IEEE Trans.
Electron Dev., 2012, 59, 1494; (d) Z. Chen, M. J. Lee, R. S.
Ashraf, Y. Gu, S. AlbertꢀSeifried, M. M. Nielsen, B.
Schroeder, T. D. Anthopoulos, M. Heeney, I. McCulloch
and H. Sirringhaus, Adv. Mater., 2012, 24, 647; (e) J. Lee,
A.ꢀR. Han, H. Yu, T. J. Shin, C. Yang and J. H. Oh, J. Am.
Chem. Soc., 2013, 135, 9540; (f) B. Sun, W. Hong, Z.
Yan, H. Aziz and Y. Li, Adv. Mater., 2014, 26, 2636.
(a) T. Lei, J.ꢀH. Dou, Z.ꢀJ. Ma, C.ꢀH. Yao, C.ꢀJ. Liu, J.ꢀY.
Wang and J. Pei, J. Am. Chem. Soc., 2012, 134, 20025; (b)
T. Lei, J.ꢀH. Dou, Z.ꢀJ. Ma, C.ꢀJ. Liu, J.ꢀY. Wang and J.
Pei, Chem. Sci., 2013, 4, 2447; (c) L. A. Estrada, R. Stalder,
K. A. Abboud, C. Risko, J.ꢀL. Bredas and J. R. Reynolds,
Macromolecules, 2013, 46, 8832.
The authors would like to express sincere gratitude to
Center for Advanced Materials Analysis, Tokyo Institute of
Technology, for Xꢀray diffraction measurements. This work
was partly supported by a Grantꢀin Aid for Scientific Research
(B) (No. 23350061) from the Ministry of Education, Culture,
Sports, Science, and Technology of Japan.
Notes and references
a
Department of Organic and Polymeric Materials, Tokyo Institute of
4
Technology, Oꢀokayama, Meguroꢀku, Tokyo, 152ꢀ8552, Japan.
b
Department of Chemistry, Tokyo Institute of Technology, 2ꢀ12ꢀ1 Oꢀ
okayama, Meguroꢀku, Tokyo 152ꢀ8551, Japan.
c ACTꢀC, JST, Honcho, Kawaguchi, Saitama 332ꢀ0012, Japan.
Eꢀmail: higashino.t.aa@m.titech.ac.jp, mori.t.ae@m.titech.ac.jp
†
Electronic supporting information (ESI) available: CCDC 1031323ꢀ
1031326 contain the supplementary crystallographic information for 2a
Additional information for synthesis, redox and optical properties,
5
6
C. Guo, B. Sun, J. Quinn, Z. Yan and Y. Li, J. Mater.
Chem. C, 2014, 2, 4289.
(a) M. IrimiaꢀVladu, E. D. Głowacki, P. A. Troshin, G.
Schwabegger, L. Leonat, D. K. Susarova, O. Krystal, M.
Ullah, Y. Kanbur, M. A. Bodea, V. F. Razumov, H. Sitter,
S. Bauer and N. S. Sariciftci, Adv. Mater., 2012, 24, 375;
ꢀ
d.
crystal structures, band calcutions, devive fabrication, and thin film
properties.
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 7 of 8
Journal of Materials Chemistry C
View Article Online
Journal Name
ARTICLE
DOI: 10.1039/C4TC02467B
(b) Y. Kanbur, M. IrimiaꢀVladu, E. D. Głowacki, G. Voss, 19 T. Kakinuma, H. Kojima, M. Ashizawa, H. Matsumoto and
M. Baumgartner, G. Schwabegger, L. Leonat, M. Ullah, H.
Sarica, S. ErtenꢀEla, R. Schwödiauer, H. Sitter, Z.
T. Mori, J. Mater. Chem. C, 2013, 1, 5395.
Küçükyavuz, S. Bauer and N. S. Sariciftci, Org. Electron.
,
2012, 13, 919; (c) E. D. Głowacki, D. H. Apaydin, Z.
Bozkurt, U. Monkowius, K. Demirak, E. Tordin, M.
Himmelsbach, C. Schwarzinger, M. Burian, R. T. Lechner,
N. Demitri, G. Vossa and N. S. Sariciftci, J. Mater. Chem.
C
, 2014, 2, 8089; (d) O. Pitayatanakul, T. Higashino, T.
Kadoya, M. Tanaka, H. Kojima, M. Ashizawa, T.
Kawamoto, H. Matsumoto, K. Ishikawa and T. Mori, J.
Mater. Chem. C, 2014, 2, 9311.
7
8
H. Kojima and T. Mori, Chem. Lett., 2013, 42, 68.
(a) D. SchulteꢀFrohlinde and F. Erhardt, Liebigs Ann.
Chem., 1963, 92; (b) H. Laatsch, Liebigs Ann. Chem., 1984,
1367; (c) H. Laatsch, Liebigs Ann. Chem., 1990, 433; (d) C.
Göltner and H. Laatsch, Liebigs Ann. Chem., 1991, 1085.
T. N. Van, B. Kesteleyn and N. D. Kimpe, Tetrahedron,
2001, 57, 4213.
9
10 M. L. Tang, A. D. Reicharrdt, P. Wei, and Z. Bao, J. Am.
Chem. Soc., 2009, 131, 5264.
11 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B.
Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X.
Li,H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J.
L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F.
Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin,
V. N. Staroverov, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E.
Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R.
Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K.
Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09
(Revision B. 01), Gaussian, Inc., Wallingford CT, 2009.
12 (a) H. Bauer, K. Kowski, H. Kuhn, W. Lüttke and P.
Rademacher, J. Mol. Struct., 1998, 445, 277; (b) L.
SerranoꢀAndrés and B. O. Roos, Chem. Eur. J., 1997, 3,
717.
13 A. N. Cammidge, V. H. M. Goddard, C. P. J. Schubert, H.
Gopee, D. L. Hughes and D. Gꢀ. Lucas, Org. Lett., 2011,
13, 6034.
14 J. R. Desiraju, Acc. Chem. Res., 1991, 24, 290.
15 H. Yanagisawa, J. Mizuguchi, S. Aramaki and Y. Sakai,
Jpn. J. Appl. Phys., 2008, 47, 4728.
16 H. L. Ammon, M. Sundaralingam and J. M. Stewart, Acta.
Cryst. B, 1969, 25, 336.
17 T. Higashino, J. Cho and T. Mori, Appl. Phys. Express
2014, , 121602.
,
7
18 J.ꢀP. Gorce, S. J. Spells, X.ꢀB. Zeng and G. Ungar, J. Phys
Chem B, 2004, 108, 3130.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 |
7

Journal of Materials Chemistry C
Page 8 of 8
View Article Online
DOI: 10.1039/C4TC02467B
The table of contents entry
Title
Ambipolar Transistor Properties of 2,2′ꢀBinaphthosemiquinones
Text (one sentence, of maximum 20 words, highlighting the novelty of the work)
Binaphthosemiquinones having characteristic blue colors owing to the small energy gaps are
proved to show ambipolar transistor properties.
Keywords
organic transistor, organic semiconductor, ambipolar transport, donorꢀacceptor
Authors
Toshiki Higashino, Shohei Kumeta, Sumika Tamura, Yoshio Ando, Ken Ohmori, Keisuke Suzuki,
and Takehiko Mori
ToC figure (maximum size 8 cm x 4 cm)