1,6- and 2,7-trans-β-Styryl Substituted Pyrenes Exhibiting Both Emissive and Semiconducting Properties in the Solid State

Article abstract of DOI:10.1021/acs.chemmater.7b00056

Molecular materials that are both emissive and semiconducting are highly demanding for organic optoelectronics. In this article, we report the synthesis, emissive, and semiconducting properties of 1,6 and 2,7-trans-β-styryl substituted pyrenes (16PyE and

Full text of DOI:10.1021/acs.chemmater.7b00056

Subscriber access provided by University of Newcastle, Australia
Article
1, 6- and 2, 7-Trans-#-Styryl Substituted Pyrenes Exhibiting
Both Emissive and Semiconducting Properties in the Solid State
Huajun Ju, Kang Wang, Jing Zhang, Hua Geng, Zitong
Liu, Guanxin Zhang, Yongsheng Zhao, and Deqing Zhang
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.7b00056 • Publication Date (Web): 07 Apr 2017
Downloaded from http://pubs.acs.org on April 9, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Chemistry of Materials is published by the American Chemical Society. 1155 Sixteenth
Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 11
Chemistry of Materials
1
2
3
4
5
6
7
8
9
1, 6ꢀ and 2, 7ꢀTransꢀβꢀStyryl Substituted Pyrenes Exhibiting Both
Emissive and Semiconducting Properties in the Solid State
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Huajun Ju, †,‡ Kang Wang, †,‡ Jing Zhang, †,‡ Hua Geng,† Zitong Liu,† Guanxin Zhang,* † Yongsheng
Zhao, †,‡ Deqing Zhang*†,‡
†Beijing National Laboratories for Molecular Sciences, CAS Key Laboratories of Organic Solids and Photochemistry
CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences,
Beijing, 100190 (P. R. China)
‡University of Chinese Academy of Sciences, Beijing, 100049 (P. R. China)
ABSTRACT: Molecular materials that are both emissive and semiconducting are highly demanding for organic optoelectronics. In
this paper, we report the synthesis, emissive and semiconducting properties of 1, 6 and 2, 7ꢀtransꢀβꢀstyryl substituted pyrenes
(16PyE and 27PyE). The results reveal that both 16PyE and 27PyE are emissive and semiconducting in the solid state. The fluoꢀ
rescence quantum yields of crystalline solids of 16PyE and 27PyE were determined to be 28.8% and 27.4%, respectively. Microꢀ
rods of 16PyE and microplates of 27PyE were found to exhibit promising optical waveguilding behavior. Furthermore, on the basis
of the transfer and output curves of the respective organic field effect transistors (OFETs), thin films of 16PyE and 27PyE were
found to show pꢀtype semiconducting property with hole mobility up to 1.66 cm2Vꢀ1sꢀ1. Such dual functions (emissive and semiꢀ
conducting) of 16PyE and 27PyE can be ascribed to the unique intermolecular interactions and packing within crystals of 16PyE
and 27PyE.
ducting with single crystal mobility of 34 cm2Vꢀ1sꢀ1.58 These
results clearly demonstrate that intermolecular interactions and
■ INTRODUCTION
Various conjugated molecules and macromolecules have been
investigated for either highly emissive materials or semiconꢀ
ductors with high charge mobilities.1–19 Such emissive materiꢀ
als and organic semiconductors have been utilized to fabricate
OLEDs (organic lightꢀemitting diodes) and OFETs (organic
fieldꢀeffect transistors), respectively. The performances of
OLEDs and OFETs have been improved significantly thanks
to the developments of i) the emissive materials with high
quantum yields and tunable emitting colors20–26 and ii) pꢀ, nꢀ
and ambipolar semiconductors with high charge mobilities.1–8,
orientations are critical for molecular solids to be strongly
emissive and semiconducting simultaneously. But, the clear
structureꢀproperty correlation has been not yet established for
such dual functional materials.
In this paper, we report 1, 6ꢀ and 2, 7ꢀtransꢀβꢀstyryl substiꢀ
tuted pyrenes (16PyE and 27PyE in Scheme 1) for the develꢀ
opment of molecular materials exhibiting both emissive and
semiconducting properties. The molecular design is based on
the following considerations: i) pyrene derivatives can be
emissive in both solution and solid state, and they can also
exhibit excimer emission under certain conditions,59–60 ii) semꢀ
iconductors with high hole mobilities have been reported with
27–43
Meanwhile, molecular materials that are both emissive
and semiconducting are highly demanding for applications in
organic light emitting fieldꢀeffect transistors15–17, 44–47 and orꢀ
ganic lasers.48, 49 However, it still remains challenging to raꢀ
tionally devise such dual functional materials. This is because
organic semiconductors usually entail intermolecular πꢀπ
stacking to generate conducting pathways, but such πꢀπ interꢀ
actions are normally detrimental to lightꢀemissions due to the
formation of excimers or exciplexes.50–53 Nevertheless, a numꢀ
ber of dual functional materials with both emissive and semiꢀ
conducting properties have been reported in recent years.54–58
For instance, some of us found that the cruciform molecule,
2,2′ꢀ((5,5′ꢀ(3,7ꢀdicyanoꢀ2,6ꢀbis(dihexylamino)benzoꢀ
pyrene derivatives,61–67 and iii) the incorporation of
βꢀstyryl
units into the pyrene core can alter the intermolecular interacꢀ
tions so that the resulting solids show both emissive and semiꢀ
conducting properties simultaneously.67 The results reveal that
the crystalline solids of 16PyE and 27PyE are dual functional
with fluorescence quantum yields and hole charge mobilities
up to 28.8% and 1.66 cm2Vꢀ1sꢀ1, respectively. Moreover, emisꢀ
sive microrods of 16PyE and microplates of 27PyE exhibit
outstanding optical waveguide behaviors.
■ RESULTS AND DISCUSSIONS
[1,2b:4,5b′]ꢀdifuranꢀ4,8
diyl)bis(thiopheneꢀ5,2ꢀ
diyl))bis(methanylylidene)) dimalonoꢀ nitrile (BDFTM)55 and
the naphthalene diimide derivatives56, 57 exhibited both emisꢀ
sive and semiconducting properties in the solid states, but their
charge mobilities were low. Heeger, Hu and their coworkers
reported 2,6ꢀsubstituted anthracene molecules which were
found to be not only highly emissive, but also pꢀtype semiconꢀ
Synthesis and crystal structures. Compounds 16PyE and
27PyE were successfully obtained by the respective Pdꢀ
catalyzed coupling reactions (see Scheme 1) of 1, 6ꢀ
dibromopyrene and 2, 7ꢀdibromopyrene with transꢀβꢀstyryl
boronic acid, followed by recrystallization from toluene, in
high yields (>80%). Both 16PyE and 27PyE show poor soluꢀ
ACS Paragon Plus Environment

Chemistry of Materials
Page 2 of 11
bility in most organic solvents, and they are only dissolved in
onset oxidation potentials (Eox.onset, vs. Fc/Fc+) of 16PyE and
1
2
3
4
5
6
7
8
hot DMF and aromatic solvents. The thermogravimetric analyꢀ
sis (see Figure S1) reveals that both 16PyE and 27PyE are
thermally stable below 250 oC.
27PyE were measured to be 0.84 V and 0.86 V, respectively.
Based on the onset potentials, HOMO energies were estimated
to be ꢀ5.64 eV for 16PyE and ꢀ5.66 eV for 27PyE, respectiveꢀ
ly. Figure S5B shows the absorption spectra of 16PyE and
27PyE in the solid states. 16PyE absorbs strongly at 420 nm
and 468 nm, whereas the maxima absorptions of 27PyE are
blueꢀshifted to 336 nm and 351 nm (see Table 1). Furtherꢀ
more, the onset absorptions of 16PyE and 27PyE were deterꢀ
mined to be 521 and 465 nm, respectively. Thus, the respecꢀ
tive optical bandgaps of 16PyE and 27PyE were estimated to
be 2.38 eV and 2.67 eV. Accordingly, the LUMO energies of
16PyE and 27PyE were calculated to be ꢀ3.26 eV and ꢀ2.99
eV, respectively, by using the equation LUMO = HOMO +
Egopt. Obviously, 16PyE shows lower LUMO level than
27PyE, which can be rationalized as follows: the styryl substiꢀ
tution at 2,7ꢀpositions is expected to have less perturbation on
the electronic properties of pyrene since nodal planes pass
through the 2,7ꢀpositions in both the HOMO and LUMO orꢀ
bitals of pyrene.59 However, the styryl substitution at the 1,6ꢀ
positions of pyrene as in 16PyE will elongate the conjugation,
and as a consequence the LUMO orbital can be stabilized.
Scheme 1. Chemical structures of 16PyE and 27PyE and
their synthetic approaches.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Single crystals of 16PyE and 27PyE suitable for Xꢀray analꢀ
ysis were obtained and their crystal structures were successfulꢀ
ly determined. Figure 1 shows their molecular structures and
intermolecular arrangements. Both 16PyE and 27PyE adopt
Eꢀconformations, and the phenyl groups in 16PyE and 27PyE
are not coplanar with the respective pyrene rings, forming
dihedral angles of 18.46o and 32.42o, respectively. As shown
in Figure S2, short interatomic C…H’ and C…C’ contacts in
the range of 2.855ꢀ3.260 Ǻ are observed for 16PyE. Apart
from the multiple short interatomic C…H’ (2.811ꢀ2.850 Ǻ)
contacts, intermolecular CꢀH…π (2.848 Ǻ) interactions are
observed for 27PyE (see Figure S3). Notably, the neighboring
pyrene units are not parallel and no intermolecular faceꢀtoꢀface
arrangements are detected; instead the neighboring pyrene
units are inclined to each other with dihedral angles ranging
from 25.51o to 34.30o. Molecules are relatively densely packed
with packing indexes of 0.686 and 0.715 within crystals of
27PyE and 16PyE, respectively. 68 As to be discussed below,
such intermolecular interaction and arrangements make these
molecular materials be semiconducting and emissive simultaꢀ
neously. The multiple intermolecular interactions can endow
16PyE and 27PyE in the solid state with semiconducting
property, whereas the fact that the neighboring pyrene and
phenyl units are not in faceꢀtoꢀface orientations is expected to
keep 16PyE and 27PyE being emissive in the solid state.
1.0
A)
16PyE
27PyE
0.8
0.6
0.4
0.2
0.0
400
500
650
450Wavelengt5h50(nm)600
1.0
0.8
0.6
0.4
0.2
0.0
B)
16PyE
27PyE
400
450
500
550
600
650
Wavelength (nm)
Figure 2. Normalized fluorescence spectra of DMF solutions (A,
10 µM) and thin films (B) of 16PyE and 27PyE.
Emissive and optical waveguiding properties. Both 16PyE
and 27PyE are emissive in solutions and solid states. As deꢀ
picted in Figure 2, solutions and thin films of 16PyE and
27PyE exhibit structured emission bands, and the respective
emission maxima, quantum yields and lifetimes are listed in
Table 1. The respective emission maxima of 16PyE in soluꢀ
tion and solid state are redꢀshifted in comparison with those of
27PyE. As discussed above, this can be attributed to the fact
that substitution at 2,7ꢀpositions has less pronounced effects
on the electronic structure of pyrene, but the styryl substitution
at the 1,6ꢀpositions of pyrene can prolong the conjugation
which will lead to the redꢀshift of the fluorescence spectrum.
The structured emission bands of 16PyE and 27PyE in the
Figure 1. (From left to right) Molecular structures, dihedral anꢀ
gles between the respective benzene ring and the pyrene core, and
the intermolecular arrangements of 16PyE (up, aꢀc) and 27PyE
(down, dꢀf).
HOMO/LUMO energies. As shown in Figure S4, 16PyE and
27PyE show one quasiꢀreversible oxidation wave at 0.82 V
and 0.98 V (Eox.1/2, vs. Fc/Fc+), respectively. The respective
ACS Paragon Plus Environment

Page 3 of 11
Chemistry of Materials
Table 1. The absorption and fluorescence data of 16PyE and 27PyE
1
2
3
4
5
6
7
8
Solution
PL
Solid State
PL
Abs.
Фa
Abs.
Фc
<τ>b
(ns)
2.0
<τ>d
λ (nm)
λem.(nm)
463, 485
(%)
λ (nm)
λem. (nm)
(%)
(ns)
16PyE
27PyE
302, 410, 434
323, 338
81.4
420, 468
336, 351
526, 565
28.8
27.4
2.9
46.7
437, 465, 497 15.2
27.6
446, 474, 502
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
a, c The quantum yields in solutions (5.0 µM in DMF) and in the solid states were measured with the Hamamatsu spectrometer C11347
QuantaurusꢀQY; b, d Fluorescence lifetimes in solutions (5.0 µM in DMF) and in the solid state were measured with the Hamamatsu specꢀ
trometer C11367.
2.0x104
0.6
c)
b)
e)
a)
0.5
0.4
0.3
0.2
0.1
10 ꢀm
1.5x104
1.0x104
1
2
3
4
5
6
0 5 101520253035
5.0x103
d
( )
ꢀ
m
0.0
50 ꢀm
450
500
550
600
650
700
Wavelength (nm)
9.0x102
d)
f)
1
2
3
4
2
6.0x102
3
1
3.0x102
0.0
4
10 ꢀm
50 ꢀm
400
450
500
550
600
650
Wavelength (nm)
Figure 3. a, d) PL images of microrods of 16PyE (a) and microplates of 27PyE (d) upon excitation with mercury lamp; b, e) PL images
upon excitation of microrods of 16PyE (b) and microplates of 27PyE (e); c) the corresponding spatially resolved PL spectra of the emisꢀ
sions that are outꢀcoupled at the end of the microrod of 16PyE; insets show the variation of the peak intensity at 530 nm vs. the propagaꢀ
tion distance for microrods of 16PyE; f) the corresponding spatially resolved PL spectra of the four edges (marked with 1–4) for 27PyE.
solid states may be relevant to the fact that there is no faceꢀtoꢀ
face intermolecular πꢀπ interactions within the crystals of
16PyE and 27PyE, and as a result the formation of excimers is
not favorable. As listed in Table 1, the average fluorescence
lifetimes of 16PyE and 27PyE are prolonged in the solid
states by comparing with those of 16PyE and 27PyE in the
respective solutions.
The emission quantum yields (Ф) of 16PyE in DMF
solution and solid state are 81.4% and 28.8%, respectively.
Thus, 16PyE exhibits aggregation caused quenching emission.
In the contrary, 27PyE displays aggregation induced enhanced
emission because the emission quantum yield of 27PyE
increase from 15.2% in DMF solution to 27.4% in the solid
state. The multiple intermolecular interactions within crystal
of 27PyE are expected to fix the conformation of 27PyE, thus
inhibiting the intramoleuclar motions and enhancing the
emission according to previous studies. 55–57, 69
16PyE and microplates of 27PyE were successfully obtained
by slowly cooling the respective hot solutions. As shown in
Figure 3, the microrods of 16PyE exhibit intense yellowꢀgreen
emission when excitation with mercury lamp. Moreover,
bright photoꢀluminescence spots are detected at the ends of the
microrods, while the remaining surfaces emit weakly. Such
photoluminescence images reveal that these microrods can
employ as active optical waveguides. On the basis of electron
diffraction pattern shown in Figure S7a, molecules of 16PyE
are packed along the [100] direction (aꢀaxis) to form the 1D
microrods. Such intermolecular arrangements will enable the
emission light generated upon excitation at certain position of
the microrod to be propagated along the microrod via energy
transfer mechanism. 21, 24, 55, 57
To investigate the light waveguiding efficiency, the
spatially resolved PL spectra were measured by locally
exciting the microrod of 16PyE with a 375 nm laser. Figure 3c
shows the photoꢀluminescence spectra at the end of a single
microrod of 16PyE under the excitations at different positions
(Figure 3b, labeled as 1–6). Obviously, the emissions at the
The solid state emissions of 16PyE and 27PyE endow the
crystalline microrods or microꢀplates of 16PyE and 27PyE
with promising optical waveguilding properties. Microrods of
ACS Paragon Plus Environment

Chemistry of Materials
Page 4 of 11
microrodꢀends become gradually weak with increasing strong emissions around the midꢀpoints of four edges. The
1
2
3
4
5
6
7
8
propagation distances. As depicted in the inset of Figure 3c,
the intensity of the outꢀcoupled emission decays almost
exponentially by prolonging the propagation distance. By
fitting the data,70, 71 the optical loss coefficient at 530 nm for
microrods of 16PyE was estimated to be 64 dBmmꢀ1. Such
optical loss can be ascribed to Rayleigh scattering due to
defects within microrods; such defects can induce the local
variation of refractive index along the microrods.72–76 As
displayed in Figures 2B and S5B, the corresponding
absorption and fluorescence spectral overlap is small for
16PyE in the crystalline state, thus selfꢀabsorption can not
contribute largely to the optical loss during the light
propagation.
propagation distances from the center of the microplate to the
midꢀpoints of edges 1 and 3 are the same. This agrees well
with the observation that emission intensity from the midꢀ
point of edge 1 is almost the same as that from edges 3. This
also holds true for edges 2 and 4. But, the propagation disꢀ
tance from the center of the microplate to either midꢀpoints of
edges 2 or 4 is slightly longer than that from the center of the
microplate to either midꢀpoints of edges 1 or 3. This may inꢀ
terpret the observation that emission intensities from the midꢀ
points of edges 1 and 3 are slightly stronger than those from
edges 2 and 4.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Thin film semiconducting properties. The semiconducting
properties of 16PyE and 27PyE were explored by fabrication
of the bottomꢀgate/bottomꢀcontact OFETs with thin films of
16PyE and 27PyE on OTS (octadecyltrichlorosilane)
modified SiO2/Si substrate. Thinꢀfilms of 16PyE and 27PyE
of about 50 nm in thickness were prepared by vapor deposition
at different substrate temperatures. The output and transfer
curves were measured and the semiconducting performance
data were summarized in Table 2.
The microplates of 27PyE contains two pairs of parallel
edges along the [110] and [110] directions, respectively,
based on the electron diffraction pattern (see Figure S7c).
Figure 3d shows the photoluminescence (PL) image of the
microplates of 27PyE. It is clear that the edges of these
microplates show brighter blueꢀemissions than the respective
surfaces, indicating that efficient optical waveguiding occurs
within microplates of 27PyE. Bright outꢀcoupled blueꢀ
emissions were detected around the respective midꢀpoints of
four edges (marked with 1ꢀ4) when the laser beam was
focused on the center of the microplate. The PL spectra from
the respective areas around the midꢀpoints of four edges were
collected (see Figure 3f). As shown in Figure 3f, the emission
intensity from the midꢀpoint of edge 1 is almost the same as
that of edge 3. Similarly, the emission intensity from edge 2 is
rather close to that from edge 4. But, the emission intensities
from edges 1 and 3 are slightly higher than those from edges 2
and 4. Figure S7d shows the intermolecular arrangements of
27PyE in the ab plane together with PL image of the microꢀ
plate upon the excitation at the center of the microplate. The
photoꢀluminescence energy from the molecule located at the
center of the microplate can be transferred to molecules at the
edges. The molecule at the center of the microplate is closer to
molecules around the midꢀpoints of the edges, leading to
As shown in Figure 4, IDS increases by applying the negative
VGS. Thus, both thinꢀfilms of 16PyE and 27PyE behave as pꢀ
type semiconductor, being in agreement with the HOMO and
LUMO energy levels of 16PyE and 27PyE as discussed above.
As listed in Table 2, hole mobilities of 16PyE and 27PyE
increase by enhancing the substrate temperature from 25 oC to
o
50 C, but they decrease by further increasing the substrate
temperature to 70 oC for both 16PyE and 27PyE.77 In comparꢀ
ison with those of 16PyE, thin film of 27PyE exhibits higher
mobility and higher Ion/off ratio. The hole mobility can reach
1.66 cm2Vꢀ1sꢀ1 with Ion/off ratio up to 108 for thin film of 27PyE
o
prepared on substrate at 50 C, whereas the maxima hole moꢀ
bility for thin film of 16PyE is only 0.17 cm2Vꢀ1sꢀ1 (see Table
2).
In order to understand the different semiconducting properꢀ
ties of 16PyE and 27PyE, their thin films were characterized
Table 2. Hole mobility (µ) including the average and maximum values, current on/off ratio (Ion/Ioff) and threshold voltage
(Vth) of OFETs with thinꢀfilms of 16PyE and 27PyE at different substrate temperatures.
Temp. (Sub.)
Ion/Ioff
Vth
µh(ave.)a
[cm2 Vꢀ1 sꢀ1]
0.040
µh(max.)
[cm2 Vꢀ1 sꢀ1]
0.046
[oC]
25
[V]
16PyE
27PyE
107
106
106
107
108
107
ꢀ15 – ꢀ20
ꢀ15 – ꢀ20
ꢀ10 – ꢀ15
ꢀ60 – ꢀ65
ꢀ55 – ꢀ60
ꢀ55 – ꢀ60
50
0.14
0.17
70
0.13
0.15
25
0.56
0.74
50
1.44
1.66
70
0.72
0.89
a The average mobilities were obtained based on more than 10 OFET devices.
ACS Paragon Plus Environment

Page 5 of 11
Chemistry of Materials
3.0x10ꢀ6
0.0032
0.0024
0.0016
0.0008
0.0000
1Eꢀ5
1Eꢀ7
0.18
0.15
0.12
0.09
0.06
0.03
0.00
1
ꢀ20 V
ꢀ30 V
ꢀ40 V
ꢀ50 V
ꢀ60 V
B)
2.5x10ꢀ6
1
2
3
4
5
6
7
8
A)
C)
3
V
DS=ꢀ100 V
2.0x10ꢀ6
1.5x10ꢀ6
1.0x10ꢀ6
2
2
2
1Eꢀ9
5.0x10ꢀ7
0.0
1Eꢀ11
ꢀ60 ꢀ50
ꢀ40
ꢀ20
ꢀ10
0
VDS (ꢀV30)
ꢀ60 ꢀ50
ꢀ10
0
10
ꢀ40 VGꢀ3S0(Vꢀ)20
Counts
6.0x10ꢀ5
5.0x10ꢀ5
4.0x10ꢀ5
3.0x10ꢀ5
2.0x10ꢀ5
0.010
0.008
0.006
0.004
0.002
0.000
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
1Eꢀ4
1Eꢀ6
1
9
ꢀ40 V
ꢀ50 V
ꢀ60 V
ꢀ70 V
ꢀ80 V
F)
E)
D)
2
3
2
1
10
11
12
13
14
15
16
17
V
DS=ꢀ100 V
1
1Eꢀ8
1Eꢀ10
1Eꢀ12
1.0x10ꢀ5
0.0
ꢀ80 ꢀ70 ꢀ60 ꢀ50 ꢀ40 ꢀ30 ꢀ20 ꢀ10
0
Counts
ꢀ80 ꢀ70 ꢀ60 ꢀ50
ꢀ30 ꢀ20 ꢀ10
VꢀG4S0(V)
0
10
VDS (V)
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 4. Output and transfer characteristics of OFETs with thin films of 16PyE (A, B) and 27PyE (D, E) deposited on OTSꢀmodified
SiO2/Si substrate at 50 °C; the channel width (W) and the lengths (L) were 1440 nm and 40 nm, respectively; histograms of device mobility
for thin films of 16PyE (C) and 27PyE (F) deposited on OTSꢀmodified SiO2/Si substrate at 50 °C.
o
with AFM and XRD. As depicted in Figure 5A, one diffracꢀ
substrate temperature to 70 C. In comparison, no diffractions
were observed for thin films of 16PyE deposited at different
temperatures as shown in Figure 5B. This agrees with the fact
that thin film of 16PyE possesses relatively low hole mobility.
tion peak at 2
θ
=5.02o was detected for thin film of 27PyE
o
deposited at 25 C. When the substrate temperature was enꢀ
o
hanced to 50 C, the diffraction intensity 5.02o increased, and
high order diffractions at 2
emerged concomitantly. The dꢀspacing corresponding to the
diffraction at 2
=5.02o is 17.5 Å, which is shorter than the
θ
=10.04o, 15.08o and 20.22o
Figure 6 depicts the AFM images of thin films of 27PyE
and 16PyE deposited at different temperatures. It is clear that
layered structures were formed after the substrate was heated
to 50 oC, and grain size was incremented from ca. 450 nm for
thin film deposited at 25 C to ca. 1100 nm. However, the
grain size was reduced to ca. 600 nm and moreover boundary
areas emerged among the grains for thin film of 27PyE deposꢀ
ited at 70 C (see Figure 6). Such thinꢀfilm morphological
alteration agrees well with the thin film semiconducting perꢀ
formance of 27PyE at different substrate temperatures (see
Table 2).
θ
molecular length of 27PyE (20.2 Å). Thus, molecules of
27PyE are probably tilted onto the surface of the substrate.
The emergence of more diffractions up to fourth orders reveals
that the thin film crystallinity increases for 27PyE upon inꢀ
creasing the substrate temperature. The thin film XRD pattern
of 27PyE was also compared with that simulated from its
o
o
crystal structural data (see Figure S9). The signals at 2θ
=5.02o,
10.04o, 15.08o and 20.22o match well with the 002, 004, 006
and 008 diffractions, respectively. The appearance of these
diffractions manifest that molecules of 27PyE are orderly
stacked along the cꢀaxis within thin film on substrate at 50 oC.
However, these diffractions were weakened after further inꢀ
For thin films of 16PyE at different substrate temperatures,
no layered structures were detected. But, the grain size inꢀ
creased by enhancing the substrate temperatures. It is expected
that large grains are beneficial for charge transporting. For thin
film of 16PyE deposited at 70 oC, there are obviously boundaꢀ
ry areas among the grains. The presence of boundary areas is
detrimental for charge transporting.
o
creasing the substrate temperature to 70 C (see Figure 5A).
These XRD data are in good agreement with the fact that thin
film hole mobility firstly increases by enhancing the substrate
temperature to 50 oC, but it decreases after further boosting the
1000
500
0
1000
500
0
B)
A)
70 o
C
70oC
50 oC
30 oC
50oC
30oC
5
10
15
20
25
30
5
10
15
20
25
30
2
θ
2
θ
Figure 5. XRD patterns of thinꢀfilms of 27PyE (A) and 16PyE (B) deposited at different substrate temperatures.
ACS Paragon Plus Environment

Chemistry of Materials
27PyE TSub.=70 oC
27PyE TSub.=50 oC
Page 6 of 11
80 nm
27PyE TSub.=25 oC
1
2
3
4
5
6
7
8
9
500 nm
500 nm
500 nm
0 nm
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
100 nm
16PyE TSub.=25 oC
16PyE TSub.=50 oC
16PyE TSub.=70 oC
1 ꢁm
1 ꢁm
1 ꢁm
0 nm
Figure 6. AFM images of thinꢀfilms of 27PyE and 16PyE deposited on OTSꢀmodified SiO2/Si substrates at different temperatures.
In addition, the bottomꢀgate/topꢀcontact OFETs with
crystalline microrods of 16PyE and microplates of 27PyE
were fabricated with the technique reported previously78,79 (see
Supporting Information), and the respective transfer and outꢀ
put characteristics were depicted in Figure S10. As expected,
both microrods of 16PyE and microplates of 27PyE display
typical pꢀtype semiconducting behavior. As listed in Table S2,
the averge/highest hole mobilities were measured to be
0.054/0.13 cm2Vꢀ1sꢀ1 for the microrods of 16PyE along [100]
direction (aꢀaxis) of the crystal. For microplates of 27PyE, the
within the crystal of 27PyE is almost isotropic. This is conꢀ
sistent with the fact that charge mobilities measured along the
two microplate edges are almost identical (see Table S2). Taꢀ
ble S3 also shows that 27PyE exhibits smaller hole reorganiꢀ
zation energy than 16PyE. This can interpret the fact that hole
mobilities of both thin film and crystalline object for 27PyE
are higher than those for 16PyE.
■ CONCLUSION
Two transꢀβꢀstyryl substituted pyrenes 16PyE and 27PyE
averge/highest hole mobilities along [110] direction were
were synthesized and characterized. The results reveal that the
incorporation of styryl groups in 16PyE and 27PyE alters the
intermolecular arrangements largely; multiple intermolecular
interactions exist within crystals of 16PyE and 27PyE, but
neighboring pyrene units are not arranged in faceꢀtoꢀface
modes. Such unique intermolecular arrangements endow
16PyE and 27PyE with both emissive and semiconducting
properties in the solid state. 16PyE and 27PyE are fluorescent
in solutions and solid states, and interestingly 27PyE exhibits
aggregation induced enhanced emission with quantum yield of
27.4% in the solid state. Furthermore, microrods of 16PyE and
microplates of 27PyE possess promising optical waveguiding
properties. Thin films of 16PyE and 27PyE deposited at
different substrate temperatures were utilized to fabricate
OFETs, and the results manifest that i) thin films of 16PyE
and 27PyE are pꢀtype semiconducting, ii) hole mobility of thin
film of 27PyE is generally higher than that of 16PyE, and iii)
the maxima charge mobility is 1.66 cm2Vꢀ1sꢀ1 for thin film of
27PyE deposited at 50 oC. It is intended to explore the
correlation between molecular structure and intermolecular
interactions and packing with the emissive and
semiconducting properties in further studies. Such structureꢀ
emissive/semiconducting property correlation will aid us to
optimize the structural design for molecular materials with
high emission quantum yields and charge mobility.
deduced to be 0.14/0.32 cm2Vꢀ1sꢀ1, whilst those along [110]
direction were 0.11/0.27 cm2Vꢀ1sꢀ1. Thus, the chargeꢀ
transporting along [110] and [110] directions is almost isoꢀ
tropic for microplates of 27PyE. It is noted that hole mobiliꢀ
ties of OFETs with crystalline microrods of 16PyE and miꢀ
croplates of 27PyE are lower than the respective ones of thin
films of 16PyE and 27PyE. This is likely owing to the high
bulk resistances induced by the relatively large thicknesses79
(80ꢀ115 nm, see Figure S10) for microrods of 16PyE and miꢀ
croplates of 27PyE.
Furthermore, intermolecular transfer integrals and hole reorꢀ
ganization energies were calculated on the basis of crystal
structures of 16PyE and 27PyE (see Figure S11), aiming to
understand the correlation between the semiconducting propꢀ
erty and intermolecular packing. As listed in Table S3, interꢀ
molecular transfer integrals along the molecular long axis of
16PyE (pathways 3 and 4 in Figure S11) are small, but the
intermolecular transfer integrals along pathways 1 and 2
(along the aꢀaxis) are large (see Table S3). These data indicate
that the crystal of 16PyE is expected to exhibit anisotropic
charge transporting behavior with high charge mobility along
the aꢀaxis, corresponding to the long axis of the microrod (see
Figure S10). For 27PyE, however, intermolecular transfer
integrals along different pathways are almost the same (see
Figure S11 and Table S3), indicating that charge transporting
■ EXPERIMENTAL SECTION
ACS Paragon Plus Environment

Page 7 of 11
Chemistry of Materials
Materials and characterization techniques. Chemicals and
room temperature. The thin film surfaces were analyzed with
tappingꢀmode AFM using Digital Instruments Nanoscope III and
V atomic force microscope in ambient conditions in the dark.
Thin films for AFM investigation were identical to those emꢀ
ployed for the fabrication of organic filedꢀeffect transistors.
General procedure for the synthesis of 16PyE and 27PyE.
To a degassed THF solution (10 mL) of 1, 6ꢀdibromopyrene or 2,
1
2
3
4
5
6
7
8
solvents were purchased from AlfaꢀAesar, SigmaꢀAldrich, J&K
and used without further purification. Solvents and other common
reagents were obtained from Beijing Chemical Co..
1H NMR and 13C NMR spectra were recorded on Bruker
AVANCE III 500 MHz spectrometer using tetramethylsilane as
internal standard. EIꢀMS spectra were recorded with APEX II
spectrometer (FTꢀICRꢀMS). Elemental analysis was performed on
a Carlo Erba model 1160 elemental analyzer. TGAꢀDTA measꢀ
urements from room temperature to 500 °C were carried out on a
SHIMADZU DTGꢀ60 instrument under a dry nitrogen flow with a
heating rate of 10 °C/min. Cyclic voltammograms were measured
on a computerꢀcontrolled CHI660C instruments at room temperaꢀ
ture; the measurements were performed in a conventional threeꢀ
electrode cell using a Pt working electrode, a Pt counter electrode
and a Ag/AgCl (saturated KCl) reference electrode, and nꢀ
Bu4NPF6 (0.1 M) as the supporting electrolyte with a scan rate of
100 mV·s−1. To calibrate the redox potentials, the cyclic voltamꢀ
mogram of ferrocene was measured under the same conditions.
Single crystals of 16PyE and 27PyE were cultivated by slowly
cooling their hot solutions in toluene. The diffraction data of sinꢀ
gle crystals were collected on Rigaku Saturn diffractometer with
CCD area detector. All calculations were performed with the
SHELXSꢀ97 programs. The crystallographic data were deposited
in the Cambridge Crystallographic Data Center (CCDC) as CCDC
1473291, CCDC 1473294 for 16PyE and 27PyE, respectively.
JASCO Vꢀ570 UVꢀVis spectrophotometer was utilized to
measure the solution and thinꢀfilm absorption spectra, while Hitaꢀ
chi (F4500) spectrophotometer was used to record the solution
7ꢀdibromopyrene (1.0 mmol) and transꢀβꢀstyrylboronic acid (5.0
mmol), a catalytic amount of [Pd(PPh3)4] and 3.0 mL of K2CO3
aqueous solution (2.0 M) were added. The mixture was heated at
o
9
80 C overnight under nitrogen atmosphere. After the reaction
mixture was cooled to room temperature, the precipitate was filꢀ
tered and washed with water. The residue was collected, dried and
then recrystallized from toluene.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
16PyE was obtained as yellow solids in 82% yield. H NMR
o
(500 MHz, DMSOꢀd6, 80 C, TMS) δ/ppm: 8.67 (d, J= 9.0, 2H),
8.45 (d, J = 8.0, 2H), 8.33ꢀ8.29 (m, 4H), 8.22 (d, J = 9.0, 2H),
7.82 (d, J = 7.5, 4H), 7.51ꢀ7.43 (m, 6H), 7.33 (t, J = 7.3, 2H); 13
C
NMR (125 MHz, DMSOꢀd6, 80 oC): δ/ppm: 138.04, 132.56,
132.48, 130.77, 129.17, 128.88, 128.29, 128.09, 127.41, 125.83,
125.74, 124.35, 123.62; EIꢀMS m/z = 406 [M+]; Anal. Calcd for
C32H22: C, 94.55; H, 5.45; found: C, 94.29; H, 5.71.
1
27PyE was obtained as white solids in 85% yield. H NMR
o
(500 MHz, DMSOꢀd6, 80 C) δ/ppm: 8.49 (s, 4H), 8.19 (s, 4H),
7.74 (d, J = 10, 4H), 7.64 (d, J = 9.2, 3H), 7.46 (t, J = 10, 4H),
o
7.34 (t, J = 10, 2H); 13C NMR (125 MHz, DMSOꢀd6, 80 C):
δ/ppm: 137.73, 135.71, 129.22, 128.22, 127.65, 127.10, 123.71;
EIꢀMS m/z = 406 [M+]; Anal. Calcd for C32H22: C, 94.55; H, 5.45;
found: C, 94.53; H, 5.47.
o
and solidꢀstate fluorescence spectra at 25 C. Fluorescence quanꢀ
■ ASSOCIATED CONTENT
Supporting Information
tum yields and fluorescence lifetimes were measured with a Haꢀ
mamatsu absolute PL quantum yield spectrometer C11347 Quanꢀ
taurusꢀQY and the compact fluorescence lifetime spectrometer
C11367 of Hamamatsu, respectively. PL images were recorded
with an Olympus research inverted system microscope equipped
with a CCD camera; a mercury lamp equipped with a bandꢀpass
filter (λ=330–380 nm) was utilized as the excitation source. To
measure the microarea PL spectra, microrods and microplates
dispersed on a glass cover slip were excited with a UV laser
(λ=375 nm, semiconductor laser). The excitation laser which was
filtered with a bandꢀpass filter (330–380 nm) was focused to exꢀ
cite the microrods and microplates with an objective lens (50×,
N.A.=0.80). The light was subsequently coupled to a grating specꢀ
trometer (Acton SPꢀ2358) and recorded by a thermal–electrically
cooled CCD (Princeton Instruments, ProEm: 1600B). TEM and
SAED measurements were carried out using a JEOLꢀ1011 transꢀ
mission electron microscope.
TGA analysis, crystallographic data, short interatomic contacts
within the crystal structures, cyclic voltammograms, absorption
spectra, fluorescence lifetime fitting curves, TEM images and
intermolecular packings, output and transfer characteristics of
OFETs of thin film deposited on OTSꢀmodified SiO2/Si substrate
at 25 °C and 75 °C, XRD patterns of thin film of 27PyE and its
simulated XRD patterns from crystal structural data, single crysꢀ
tal OFET measurement, theoretical calculation and NMR spectra.
The Supporting Information is available free of charge on the
ACS Publications website.
■ AUTHOR INFORMATION
Corresponding Author
For the fabrication of bottomꢀgate/bottomꢀcontact OFETs, a nꢀ
type Si wafer with a SiO2 layer of 300 nm and a capacitance of 11
nF cmꢀ2 were used as the gate and dielectric, respectively. Photoꢀ
lithography was employed to prepare the drainꢀsource (DꢀS) gold
contacts. Molecules of 16PyE and 27PyE (about 50 nm in thickꢀ
ness) were deposited (0.1 Å/s) under vacuum onto the Si/SiO2
substrate, which was modified by OTS at different substrate temꢀ
peratures (25 °C, 50 °C and 70 °C). The measurements were conꢀ
tacted under nitrogen atmosphere with a Keithley 4200 SCS semiꢀ
conductor parameter analyzer at room temperature. The mobility
was extracted with the following equation:
* Eꢀmails: dqzhang@iccas.ac.cn; gxzhang@iccas.ac.cn
Author Contributions
All authors have given approval to the final version of the
manuscript.
ACKNOWLEDGMENT
The present research was financially supported by the followig
projects: 21422207, 51273204, 21372226, 21661132006,
XDB12010300 and 2013CB933501. We thank Prof. Lang Jiang
for kind help on single crystal OFET measurement.
W
2
IDS
=
ꢀCi
(
VGS −Vth
)
REFERENCES
(1) Bao, Z.; Locklin, J. Organic FieldꢀEffect Transistors; CRC
Press: Boca Raton, 2007.
(2) Murphy, A. R.; Frechet, J. M. J. Organic Semiconducting
Oligomers for Use in Thin Film Transistors. Chem. Rev.
2007, 107,1066–1096.
2L
where µ is the fieldꢀeffect mobility, L and W are the channel
length and width, respectively, Ci is the insulator capacitance per
unit area, and VGS and Vth is the gate and threshold voltages, reꢀ
spectively.
The reflection mode Xꢀray diffraction (XRD) measurements
were performed with a 2ꢀkW Rigaku Xꢀray diffraction system at
ACS Paragon Plus Environment

Chemistry of Materials
Page 8 of 11
(3) Stalder, R.; Mei, J.; Graham, K. R.; Estrada, L. A.; Reynolds
ing With Counter Anions and Application for Optical Waveꢀ
1
2
3
4
5
6
7
8
J. R. Isoindigo, a Versatile ElectronꢀDeficient Unit For Highꢀ
Performance Organic Electronics. Chem. Mater. 2014, 26,
664−678.
guides. Small 2015, 11, 1335–1344.
(22) Zhang, J. N.; Kang, H.; Li, N.; Zhou, S. M.; Sun, H. M.; Yin,
S. W.; Zhao, N.; Tang, B. Z. Organic Solid Fluorophores
Regulated By Subtle Structure Modification: ColorꢀTunable
and AggregationꢀInduced Emission. Chem. Sci. 2017, 8,
577–582.
(23) Dong, Y.; Xu, B.; Zhang, J.; Tan, X.; Wang, L.; Chen, J.; Lv,
H.; Wen, S.; Li, B.; Ye, L.; Zou, B.; Tian, W. Piezochromic
Luminescence Based on The Molecular Aggregation of 9,
10ꢀBis ((E)ꢀ2ꢀ(Pyridꢀ2ꢀyl) Vinyl) Anthracene. Angew. Chem.,
Int. Ed. 2012, 51, 10782–10785.
(24) Gu, X. G.; Yao, J. J.; Zhang, G. X.; Yan, Y. L.; Zhang, C.;
Peng, Q.; Liao, Q.; Wu, Y. S.; Xu, Z. Z.; Zhao, Y. S.; Fu, H.
B.; Zhang, D. Q. PolymorphismꢀDependent Emission for Di
(pꢀMethoxylphenyl) Dibenzofulvene and Analogues: Optical
Waveguide/Amplified Spontaneous Emission Behaviors. Adv.
Funct. Mater. 2012, 22, 4862–4872.
(25) Zhao, N.; Yang, Z.; Lam, J. W. Y.; Sung, H. H. Y.; Xie, N.;
Chen, S.; Su, H.; Gao, M.; Williams, I. D.; Wong, K. S.;
Tang, B. Z. BenzothiazoliumꢀFunctionalized Tetraꢀ
phenylethene: an AIE Luminogen with Tunable SolidꢀState
Emission. Chem. Commun. 2012, 48, 8637–8639.
(26) Wang, Y.; Zhang, G.; Zhang, W.; Wang, X.; Wu, Y.; Liang,
T.; Hao, X.; Fu, H.; Zhao, Y.; Zhang, D. Tuning the Solid
State Emission of The Carbazole and CyanoꢀSubstituted
Tetraphenylethylene by CoꢀCrystallization with Solvents.
Small 2016, 12, 6554–6561.
(27) Yao, J.; Yu, C.; Liu, Z.; Luo, H.; Yang, Y.; Zhang, G.;
Zhang, D. Significant Improvement of Semiconducting Perꢀ
formance of the DiketopyrrolopyrroleꢀQuaterthiophene Conꢀ
jugated Polymer through SideꢀChain Engineering via Hydroꢀ
genꢀBonding. J. Am. Chem. Soc. 2016, 138, 173–185.
(28) Luo, H.; Yu, C.; Liu, Z.; Zhang, G.; Geng, H.; Yi, Y.; Broch,
K.; Hu, Y.; Sadhanala, A.; Jiang, L.; Qi, P.; Cai, Z.; Sirringꢀ
haus, H.; Zhang, D. Remarkable Enhancement of Charge
Carrier Mobility of Conjugated Polymer FieldꢀEffect Tranꢀ
sistors upon Incorporating an Ionic Additive. Sci. Adv. 2016,
2, e1600076.
(29) Kang, I.; Yun, H. J.; Chung, D. S.; Kwon, S. K.; Kim, Y. H.
Record High Hole Mobility in Polymer Semiconductors via
SideꢀChain Engineering. J. Am. Chem. Soc. 2013, 135,
14896–14899.
(30) Mori, T.; Nishimura, T.; Yamamoto, T.; Doi, I.; Miyazaki, E.;
Osaka, I.; Takimiya, K. Consecutive ThiopheneꢀAnnulation
Approach to πꢀExtended ThienoaceneꢀBased Organic Semiꢀ
conductors with [1]Benzothieno[3, 2ꢀb][1] benzoꢀ thiophene
(BTBT) Substructure. J. Am. Chem. Soc. 2013, 135, 13900–
13913.
(4) Guo, X.; Facchetti, A.; Marks, T. J. Imideꢀ and Amideꢀ
Functionalized Polymer Semiconductors. Chem. Rev. 2014,
114, 8943–9021.
(5) Anthony, J. E.; Facchetti, A.; Heeney, M.; Marder, S. R.;
Zhan, X. W. n-Type Organic Semiconductors in Organic
Electronics. Adv. Mater. 2010, 22, 3876–3892.
(6) Mei, J.; Diao, Y.; Appleton, A. L.; Fang, L.; Bao, Z. Inteꢀ
grated Materials Design of Organic Semiconductors for
FieldꢀEffect Transistors. J. Am. Chem. Soc. 2013, 135, 6724–
6746.
(7) Liu, Z.; Zhang, G.; Cai, Z.; Chen, X.; Luo, H.; Li, Y.; Wang,
J.; Zhang, D. New Organic Semiconductors with Imꢀ
ide/Amide-Containing Molecular Systems. Adv. Mater. 2014,
26, 6965–6977.
(8) Gao, X.; Zhao, Z. High mobility organic semiconductors for
fieldꢀeffect transistors. Sci. China Chem. 2015, 58, 947–968.
(9) Morteani, A. C.; Friend, R. H.; Silva, C. Orgainc Lightꢀ
Emitting Devices; WileyꢀVCH: Weinheim, 2006.
(10) Liu, M. S.; Niu, Y. H.; Ka, J. W.; Yip, H. L.; Huang, F.; Luo,
J.; kim, T. D.; Jen, A. K. Y. Thermally CrossꢀLinkable Holeꢀ
Transporting Materials For Improving Hole Injection In Mulꢀ
tilayer BlueꢀEmitting Phosphorescent Polymer Lightꢀ
Emitting Diodes. Macromolecules 2008, 41, 9570–9580.
(11) Zhao, Y.; Fu, H.; Peng, A.; Ma, Y.; Liao, Q.; Yao, J. Conꢀ
struction and Optoelectronic Properties of Organic Oneꢀ
Dimensional Nanostructures. Acc. Chem. Res. 2010, 43,
409–418.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(12) Qin, A.; Tang, B. Z. AggregationꢀInduced Emission: Funꢀ
damentals; Wiley: New York, 2013.
(13) Peng, Q.; Li, W.; Zhang, S.; Chen, P.; Li, F.; Ma, Y. Eviꢀ
dence of the Reverse Intersystem Crossing in Intraꢀ
Molecular ChargeꢀTransfer FluorescenceꢀBased Organic
LightꢀEmitting Devices Through Magneto Electroluminesꢀ
cence Measurements. Adv. Opt. Mater. 2013, 5, 362–366.
(14) Yu, T.; Liu, L.; Xie, Z.; Ma, Y. Progress In Small Molecule
Luminescent Materials For Organic LightꢀEmitting Diodes.
Sci. China Chem. 2015, 58, 907–915.
(15) Smits, E. C. P.; Setayesh, S.; Anthopoulos, T. D.; Buechel,
M.; Nijssen, W.; Coehoorn, R.; Blom, P. W. M.; de Boer, B.;
de Leeuw, D. M. NearꢀInfrared LightꢀEmitting Ambipolar
Organic FieldꢀEffect Transistors. Adv. Mater. 2007, 19, 734–
738.
(16) Takenobu, T.; Bisri, S. Z.; Takahashi, T.; Yahiro, M.; Adachi,
C.; Iwasa, Y. High Current Density in LightꢀEmitting Tranꢀ
sistors of Organic Single Crystals. Phys. Rev. Lett. 2008, 100,
066601.
(17) Capelli, R.; Toffanin, S.; Generali, G.; Usta, H.; Facchtti, A.;
Muccini, M. Organic LightꢀEmitting Transistors with an Efꢀ
ficiency That Outperforms the Equivalent LightꢀEmitting
Diodes. Nat. Mater. 2010, 9, 496–503.
(18) Babu, S. S.; Prasanthkumar, S.; Ajayaghosh, A. Selfꢀ
Assembled Gelators for Organic Electronics. Angew. Chem.,
Int. Ed. 2012, 51, 1766ꢀ1776.
(19) Gsänger, M.; Bialas, D.; Huang, L.; Stolte, M.; Würthner, F.
Organic Semiconductors Based on Dyes and Color Pigments.
Adv. Mater. 2016, 28, 3615–3645.
(20) Gu, X.; Yao, J.; Zhang, G.; Zhang, D. Controllable Selfꢀ
Assembly of Di (pꢀMethoxylphenyl) Dibenzofulvene into
Three Different Emission Forms. Small 2012, 8, 3406–3411.
(21) Hu, F.; Zhang, G.; Zhan, C.; Zhang, W.; Yan, Y.; Zhao, Y.;
Fu, H.; Zhang, D. Highly Solid State Emissive Pyridinium
Substituted Tetraphenylethylene Salts: Emission Color Tunꢀ
(31) Nair, V. S.; Sun, J.; Qi, P.; Yang, S.; Liu, Z.; Zhang, D.;
Ajayaghosh, A. Conjugated Random DonorꢀAcceptor Coꢀ
polymers Of [1]Benzothieno[3, 2ꢀb]Benzothiophene and
Diketopyrrolopyrrole Units for High Performance Polymeric
Semiconductor Applications. Macromolecules 2016, 49,
6334–6342.
(32) Geng, Y.; Pfattner, R.; Campos, A.; Wang, W.; Jeannin, O.;
Hauser, J.; Puigdollers, J.; Bromley, S. T.; Decurtins, S.;
Veciana, J.; Rovira, C.; MasꢀTorrent, M.; Liu, S. X. HOMO
Stabilisation in πꢀExtended Dibenzotetrathiafulvalene Derivꢀ
atives for Their Application in Organic FieldꢀEffect Transisꢀ
tors. Chem. Eur. J. 2014, 20, 16672–16679.
(33) Lei, T.; Dou, J.; Cao, X.; Wang, J.; Pei, J. Electronꢀ
Deficient Poly(pꢀphenylene vinylene) Provides Electron Moꢀ
bility over 1 cm2 V–1 s–1 under Ambient Conditions. J. Am.
Chem. Soc. 2013, 135, 12168–12171.
(34) Li, H.; Kim, F.; Ren, G.; Jenekhe, S. HighꢀMobility nꢀType
Conjugated Polymers Based on ElectronꢀDeficient
ACS Paragon Plus Environment

Page 9 of 11
Chemistry of Materials
Tetraazabenzodifluoranthene Diimide for Organic Electronꢀ
ics. J. Am. Chem. Soc. 2013, 135, 14920–14923.
(50) Birks, J. B. Photophysics of Aromatic Molecules; Wiley:
London, 1970.
1
(35) Gao, X.; Di, C.; Hu, Y.; Yang, X.; Fan, H.; Zhang, F.; Liu,
Y.; Li, H.; Zhu, D. CoreꢀExpanded Naphthalene Diimides
Fused with 2ꢀ(1,3ꢀDithiolꢀ2ꢀYlidene)Malonitrile Groups for
HighꢀPerformance, AmbientꢀStable, SolutionꢀProcessed nꢀ
Channel Organic Thin Film Transistors. J. Am. Chem. Soc.
2010, 132, 3697–3699.
(36) Nakano, M.; Osaka, I.; Hashizume, D.; Takimiya, K. αꢀ
Modified Naphthodithiophene Diimides–Molecular Design
Strategy for AirꢀStable nꢀChannel Organic Semiconductors.
Chem. Mater. 2015, 27, 6418–6425;
(37) Wang, C.; Zhang, J.; Long, G.; Aratani, N.; Yamada, H.;
Zhao, Y.; Zhang, Q. Synthesis, Structure, and Airꢀstable Nꢀ
type FieldꢀEffect Transistor Behaviors of Functionalized Ocꢀ
taazanonaceneꢀ8, 19ꢀdione. Angew. Chem., Int. Ed. 2015, 54,
6292–6296.
(38) Fukutomi, Y.; Nakano, M.; Hu, J. Y.; Osaka, I.; Takimiya, K.
Naphthodithiophenediimide (NDTI): Synthesis, Structure,
and Applications. J. Am. Chem. Soc. 2013, 135, 11445–
11448.
(39) He, T.; Stolte, M.; Würthner, F. AirꢀStable nꢀChannel Orꢀ
ganic Single Crystal FieldꢀEffect Transistors Based on Miꢀ
croribbons of CoreꢀChlorinated Naphthalene Diimide. Adv.
Mater. 2013, 25, 6951–6955.
(40) Lei, T.; Dou, J.; Ma, Z.; Yao, C.; Liu, C.; Wang, J.; Pei, J.
Ambipolar Polymer FieldꢀEffect Transistors Based on Fluorꢀ
inated Isoindigo: High Performance and Improved Ambient
Stability. J. Am. Chem. Soc. 2012, 134, 20025–20028.
(41) Amacher, A.; Luo, H.; Liu, Z.; Bircher, M.; Cascella, M.;
Hauser, J.; Decurtins, S.; Zhang, D.; Liu, S. X. Electronic
tuning effects via cyano substitution of a fused tetrathiafulvaꢀ
lene–benzothiadiazole dyad for ambipolar transport properꢀ
ties. RSC Adv. 2014, 4, 2873–2878.
(42) Yang, S.; Liu, Z.; Cai, Z.; Luo, H.; Qi, P.; Zhang, G.; Zhang,
D. Conjugated DonorꢀAcceptor Polymers Entailing Pechꢀ
mann DyeꢀDerived Acceptor with SiloxaneꢀTerminated Side
Chains Exhibiting Balanced Ambipolar Semiconducting Beꢀ
havior. Macromolecules 2016, 49, 5857–5865.
(43) Nakano, M.; Takimiya, K. Sodium SulfideꢀPromoted Thioꢀ
pheneꢀAnnulations: Powerful Tools for Elaborating Organic
Semiconducting Materials. Chem. Mater. 2017, 29, 256–264.
(44) Zaumseil, J.; Donley, C. L.; Kim, J. S.; Friend, R. H.;
Sirringhaus, H. Efficient TopꢀGate, Ambipolar, Lightꢀ
Emitting FieldꢀEffect Transistors Based on a GreenꢀLightꢀ
Emitting Polyfluorene. Adv. Mater. 2006, 18, 2708–2712.
(45) Cicoira, F.; Santato, C. Organic light emitting field effect
transistors: advances and perspectives. Adv. Funct. Mater.
2007, 17, 3421–3434.
(51) Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning,
A. P. H. About Supramolecular Assemblies of πꢀConjugated
Systems. Chem. Rev. 2005, 105, 1491–1546.
(52) Thomas III, S. W.; Joly, G. D.; Swager, T. M. Chemical
Sensors Based on Amplifying Fluorescent Conjugated Polyꢀ
mers. Chem. Rev. 2007, 107, 1339–1386.
(53) Liu, Z.; Zhang, G.; Zhang, D. Molecular Materials That can
Both Emit Light and Conduct Charges: Strategies and Perꢀ
spectives. Chem. Eur. J. 2016, 22, 462–471.
(54) Deng, J.; Xu, Y.; Liu, L.; Feng, C.; Tang, J.; Gao, Y.; Wang,
Y.; Yang, B.; Lu, P.; Yang, W.; Ma, Y. An Ambipolar Orꢀ
ganic FieldꢀEffect Transistor Based on an AIEꢀActive Single
Crystal with a High Mobility Level of 2.0 cm2 V−1 s−1. Chem.
Commun. 2016, 52, 2370–2373.
(55) Luo, H.; Chen, S.; Liu, Z.; Zhang, C.; Cai, Z.; Chen, X.;
Zhang, G.; Zhao, Y.; Decurtins, S.; Liu, S. X.; Zhang, D. A
Cruciform Electron DonorꢀAcceptor Semiconductor with
SolidꢀState Red Emission: 1D/2D Optical Waveguides and
Highly Sensitive/Selective Detection of H2S Gas. Adv. Funct.
Mater. 2014, 24, 4250–4258.
(56) Li, Y.; Zhang, G.; Yang, G.; Guo, Y.; Di, C.; Chen, X.; Liu,
Z.; Liu, H.; Xu, Z.; Xu, W.; Fu, H.; Zhang, D. Extended
πꢀConjugated Molecules Derived from Naphthalene
Diimides toward Organic Emissive and Semiconducting Maꢀ
terials. J. Org. Chem. 2013, 78, 2926–2934.
(57) Li, Y.; Zhang, G.; Zhang, W.; Wang, J.; Chen, X.; Liu, Z.;
Yan, Y.; Zhao, Y.; Zhang, D. ArylacetyleneꢀSubstituted
Naphthalene Diimides with Dual Functions: Optical Waveꢀ
guides and nꢀType Semiconductors. Chem. Asian J. 2014, 9,
3207–3214.
(58) Liu, J.; Zhang, H.; Dong, H.; Meng, L.; Jiang, L.; Wang, Y.;
Yu, J.; Sun, Y.; Hu, W.; Heeger, A. J. High mobility emisꢀ
sive organic semiconductor. Nat. Commun. 2015, 6, 10032.
(59) FigueiraꢀDuarte, T. M.; Müllen, K. PyreneꢀBased Materials
for Organic Electronics. Chem. Rev. 2011, 111, 7260–7314.
(60) Feng, X.; Hu, J. Y.; Redshaw, C.; Yamato, T. Functionalizaꢀ
tion of Pyrene to Prepare Luminescent Materials–Typical
Examples of Synthetic Methodology. Chem. Eur. J. 2016, 22,
11898–11916.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(61) Gong, Y.; Zhan, X.; Li, Q.; Li, Z. Progress Of PyreneꢀBased
Organic Semiconductor in Organic field Effect Transistor.
Sci. China Chem. 2016, 59, 1623–1631.
(62) Wang, Y.; Wang, H.; Liu, Y.; Di, C.; Sun, Y.; Wu, W.; Yu,
G.; Zhang, D.; Zhu, D. 1ꢀImino Nitroxide Pyrene for High
Performance Organic FieldꢀEffect Transistors with Low Opꢀ
erating Voltage. J. Am. Chem. Soc. 2006, 128, 13058–13059.
(63) Zhan, X.; Zhang, J.; Tang, S.; Lin, Y.; Zhao, M.; Yang, J.;
Zhang, H.; Peng, Q.; Yu, G.; Li, Z. Pyrene Fused Perylene
Diimides: Synthesis, Characterization and Applications in
Organic FieldꢀEffect Transistors and Optical Limiting with
High Performance. Chem. Commun. 2015, 51, 7156–7159.
(64) Oniwa, K.; Kikuchi, H.; Shimotani, H.; Ikeda, S.; Asao, N.;
Yamamoto, Y.; Tanigaki, K.; Jin, T. 2ꢀPositional Pyrene
EndꢀCapped Oligothiophenes for High Performance Organic
Field Effect Transistors. Chem. Commun. 2016, 52, 4800–
4803.
(65) Zöphel, L.; Beckmann, D.; Enkelmann, V.; Chercka, D.;
Rieger, R.; Müllen, K. Asymmetric Pyrene Derivatives for
Organic FieldꢀEffect Transistors. Chem. Commun. 2011, 47,
6960–6962.
(66) Cho, H.; Lee, S.; Cho, N. S.; Jabbour, G. E.; Kwak, J.;
Hwang, D. H.; Lee, C. HighꢀMobility PyreneꢀBased Semiꢀ
conductor for Organic ThinꢀFilm Transistors. ACS Appl.
Mater. Interfaces 2013, 5, 3855–3860.
(46) Seo, H. S.; Kim, D. K.; Oh, J. D.; Shin, E. S.; Choi, J. H.
Organic LightꢀEmitting FieldꢀEffect Transistors Based upon
Pentacene and Perylene. J. Phys. Chem. C 2013, 117, 4764–
4770.
(47) Głowacki, E. D.; Romanazzi, G.; Yumusak, C.; Coskun, H.;
Monkowius, U.; Voss, G.; Burian, M.; Lechner, R. T.;
Demitri, N.; Redhammer, G. J.; Sünger, N.; Suranna, G. P.;
Sariciftci, S. EpindolidionesꢀVersatile and Stable Hydrogen
Bonded Pigments for Organic FieldꢀEffect Transistors and
LightꢀEmitting Diodes. Adv. Funct. Mater. 2015, 25, 776–
787.
(48) Zhang, W.; Yao, J.; Zhao, Y. S. Organic Micro/Nanoscale
Lasers. Acc. Chem. Res. 2016, 49, 1691–1700.
(49) Zhang, C.; Zou, C. L.; Zhao, Y.; Dong, C. H.; Wei, C.; Wang,
H.; Liu, Y.; Guo, G. C.; Yao, J.; Zhao, Y. S. Organic Printed
Photonics: from Microring Lasers to Integrated Circuits. Sci.
Adv. 2015, 1, e1500257.
ACS Paragon Plus Environment

Chemistry of Materials
Page 10 of 11
(67) Moggia, F.; VidelotꢀAckermann, C.; Ackermann, J.; Raynal,
1
2
3
P.; Brisset, H.; Fages, F. Synthesis and Thin Film Electronꢀ
ic Properties of Two PyreneꢀSubstituted Oligothiophene Deꢀ
rivatives. J. Mater. Chem. 2006, 16, 2380–2386.
(68) The packing indexes was calculated with the program
PLATON, see reference: Kitajgorodskij, A. I.; Molecular
Crystals and Molecules, NewꢀYork, Academic Press, 1973.
(69) An, B. K.; Gierschner, J.; Park, S. Y. πꢀConjugated Cyꢀ
anostilbene Derivatives: A Unique SelfꢀAssembly Motif for
Molecular Nanostructures with Enhanced Emission and
Transport. Acc. Chem. Res. 2012, 45, 544–554.
4
5
6
7
8
9
(70) Yao, W.; Yan, Y.; Xue, L.; Zhang, C.; Li, G.; Zheng, Q.;
Zhao, Y.; Jiang, H.; Yao, J. Controlling the Structures and
Photonic Properties of Organic Nanomaterials by Molecular
Design. Angew. Chem. Int. Ed. 2013, 52, 8713–8717.
(71) Chen, S.; Chen, N.; Yan, Y.; Liu, T.; Yu, Y.; Li, Y.; Liu, H.;
Zhao, Y.; Li, Y. Controlling Growth of Molecular Crystal
Aggregates for Efficient Optical Waveguides. Chem. Comꢀ
mun. 2012, 48, 9011–9013.
(72) Tong, L. M.; Gattass, R. R.; Ashcom, J. B.; He, S. L.; Lou, J.
Y.; Shen, M. Y.; Maxwell, I.; Mazur, E. Subwavelengthꢀ
Diameter Silica Wires for LowꢀLoss Optical Wave Guiding.
Nature 2003, 426, 816–819.
(73) Zhang, C.; Zhao, Y. S.; Yao, J. N. Optical Waveguides at
Micro/Nanoscale Based on Functional Small Organic Moleꢀ
cules. Phys. Chem. Chem. Phys. 2011, 13, 9060–9073.
(74) Liao, Q.; Fu, H. B.; Yao, J. N. Waveguide Modulator by
Energy Remote Relay from Binary Organic Crystalline Miꢀ
crotubes. Adv. Mater. 2009, 21, 4153–4157.
(75) Zheng, J. Y.; Yan, Y. L.; Wang, X. P.; Zhao, Y. S.; Huang, J.
X.; Yao, J. N. WireꢀonꢀWire Growth of Fluorescent Organic
Heterojunctions. J. Am. Chem. Soc. 2012, 134, 2880–2883.
(76) Yan, Y.; Zhao, Y. S. Organic Nanophotonics: From Conꢀ
trollable Assembly of Functional Molecules to Lowꢀ
Dimensional Materials with Desired Photonic Properties.
Chem. Soc. Rev. 2014, 43, 4325–4340.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(77) The relatively large Vth, in particularly for thin film of 27PyE,
is likely due to the influences of interfacial structures beꢀ
tween the semiconductors and insulators.
(78) Tang, Q.; Tong, Y.; Li, H.; Ji, Z.; Li, L.; Hu, W.; Liu, Y.;
Zhu, D. HighꢀPerformance AirꢀStable Bipolar FieldꢀEffect
Transistors of Organic SingleꢀCrystalline Ribbons with an
AirꢀGap Dielectric. Adv. Mater. 2008, 20, 1511–1515.
(79) Jiang, L.; Hu, W.; Wei, Z.; Xu, W.; Meng, H. Highꢀ
Performance Organic SingleꢀCrystal Transistors and Digital
Inverters of an Anthracene Derivative. Adv. Mater. 2009, 21,
3649–3653.
ACS Paragon Plus Environment

Page 11 of 11
Chemistry of Materials
1
2
3
Table of Contents
4
5
Фmax.=28.8%
6
7
8
9
10
11
12
13
14
15
ꢀ
max.=1.66cm2Vꢀ1sꢀ1
Both 1, 6 and 2, 7ꢀtransꢀβꢀstyryl substituted pyrenes show relatively strong emissions in the solid state, and their microcrysꢀ
talline samples exhibit promising optical waveguilding behavior. Moreover, their thin films exhibit pꢀtype semiconducting
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
property with hole mobilities up to 1.66 cm2Vꢀ1sꢀ1.
ACS Paragon Plus Environment