Dicyano-substituted 2,3-naphthalimide: Synthesis and optoelectronic properties

Article abstract of DOI:10.1016/j.dyepig.2019.107564

Organic semiconductors (OSCs) have been attracted intensive academic and commercial interest due to their intriguing optoelectronic properties and potential applications for electronics. However, the development of n-type OSCs has significantly lagged beh

Full text of DOI:10.1016/j.dyepig.2019.107564

Accepted Manuscript
Dicyano-substituted 2,3-naphthalimide: Synthesis and optoelectronic properties
Jinling Li, Haowei Lin, Jie Huang, Jun Yin
PII:
S0143-7208(19)30053-1
DOI:
https://doi.org/10.1016/j.dyepig.2019.107564
Article Number: 107564
Reference:
DYPI 107564
To appear in: Dyes and Pigments
Received Date: 9 January 2019
Revised Date: 15 April 2019
Accepted Date: 14 May 2019
Please cite this article as: Li J, Lin H, Huang J, Yin J, Dicyano-substituted 2,3-naphthalimide:
Synthesis and optoelectronic properties, Dyes and Pigments (2019), doi: https://doi.org/10.1016/
j.dyepig.2019.107564.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
FULL PAPER
Dicyano-substituted 2,3-Naphthalimide: Synthesis and Optoelectronic
Properties
a*
a
b
b*
Jinling Li, Haowei Lin, Jie Huang, Jun Yin
a
b
School of Material Science & Engineering, Henan University of Technology, Zheng Zhou, 450001, China
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China
Normal University, Wuhan 430079, China
Organic semiconductors (OSCs) have been attracted intensive academic and commercial interest due to their
intriguing optoelectronic properties and potential applications for electronics. However, the development of n-type
OSCs has significantly lagged behind that of p-type counterparts. One general approach towards n-type OSCs is to
attach electron-withdrawing cyano or/and imide groups onto the typical p-type OSCs. Here we report the synthesis
and optoelectronic properties of three dicyano-substituted 2,3-naphthalimide derivatives. Their low-lying LUMO
energy levels from -3.29 to -3.37 eV made them potential candidates for n-type OSCs.
Keywords Organic semiconductor, electron-withdrawing, Dicyano-substituted 2,3-Naphthalimide
Introduction
fluorescent chemosensor and organic semiconductor,
while the attention on its another isomer
Organic semiconductors (OSCs) have been attracted
intensive academic and commercial interest due to their
intriguing optoelectronic [ properties and potential
2
,3-naphthalimide II containing a five-membered imide
[10]
ring was considerably more rare.
Motivated by the
[11]
aforementioned advancements and our previous work,
herein, we report the efficient synthesis of
dicyano-substituted 2,3-naphthalimide 1a-c (Figure 1),
which exhibited desirable electronic properties and can
1]
applications for electronics. Although both p-type and
n-type OSCs with comparable performance are required
for ambipolar transistors, p-n junctions and organic
complementary circuits, the development of n-type
OSCs has significantly lagged behind that of p-type
be used as potential n-type OSCs candidates.
R
[2]
O
O
counterparts. There is no doubt that providing more
O
N
O
NC
NC
[3]
n-type candidates is required. One general approach
towards n-type OSCs is to attach electron-withdrawing
cyano or/and imide groups onto the typical p-type
N
R
N R
O
O
I
II
1a-c
[4]
OSCs. Introducing electron-withdrawing groups can
decrease the unoccupied molecular orbital (LUMO)
energy level and improve the efficiency of electron
Figure 1 Structure of 1,8-naphthalimide (I), 2,3-naphthalimide
II), dicyano-substituted 2,3-naphthalimide 1a-c
(
[5]
transport. For example, imide group not only lower
LUMO level but also provides a position to introduce
alkyl chains which will both ensure sufficient solubility
of the resulted molecule and may also lead to a closer
Experimental
2
.1. Instruments and reagents
[
6]
stacking distance. Based on this design concept, Wu
reported dicyano-substituted ovalene diimides (ODI) as
a solution-processible n-type OSCs for air stable
General: 3, 4 and 5 have been reported in the
[11a, 12-14]
literatures.
All manipulations were carried out
under an argon atmosphere by using standard Schlenk
techniques, unless otherwise stated. All commercials
[
7]
field-effect
transistors.
Marks
reported
1
dicyano-substituted perylene diimide (PDI) derivatives
with LUMO level below -4,3 eV, that also appeared to
have good air stability and excellent n-channel
performance in ambient conditions. As well as Chi
reported a series of cyanated naphthalene diimide (NDI)
derivatives with a lowered LUMO levels. We are
particularly interested in naphthalimide structure. In the
past decade, its isomer 1,8-naphthalimide I containing a
six-membered imide ring has been frequently applied in
supramolecular and materials chemistry, for instance, as
were used as received without further purification. H
1
3
and C NMR spectra were collected on a 400 or 600
MHz spectrometer. UV−vis and fluorescence spectra
were obtained on a UV or fluorescent spectrophotometer.
Mass spectra were measured in the EI mode. Cyclic
voltammetry (CV) was performed on a potentiostat. A
three-electrode one-compartment cell was used to
contain the solution of complexes and supporting
electrolyte in dry CH Cl . Deaeration of the solution
[8]
[9]
2
2
was achieved by bubbling argon through the solution for
*
E-mail: jinling_li@haut.edu.cn; yinj@mail.ccnu.edu.cn; Tel.: +86-0371-67758722; Fax: +86-27-67867725
Received ((will be filled in by the editorial staff)); revised ((will be filled in by the editorial staff)); accepted ((will be filled in by the editorial staff)).
Supporting information for this article is available from the author.

ACCEPTED MANUSCRIPT
about 10 min before measurement. The ligand and
electrolyte (n-Bu NPF ) concentrations were typically
chloroform and THF. The chemical structures of 1a-c
were clearly verified by standard spectroscopic
characterizations such as NMR spectroscopy and mass
4
6
0
.001 and 0.1 M, respectively. A 500 µm diameter
platinum disk working electrode, a platinum wire
spectrometry (see the supporting information).
+
Br
counter electrode, and an Ag/Ag reference electrode
Br
CN
NC
+
Br2,I2
CuCN
75%
Br
2
Br
Br
were used. The Ag/Ag reference electrode contained an
90%
75%
internal solution of 0.01 M AgNO in acetonitrile and
Br
CN
NC
3
2
3
4
5
Br
was incorporated into the cell with a salt bridge
containing 0.1 M n-Bu NPF in CH Cl .
R
N
4
6
2
2
O
O
O
NC
NC
4 9
a:R=n-C H
N
R
b:R=n-C H
2
.2 Synthesis
8 17
c:R= CH(C
2 5 2
H )
NaI,70-85%
1a-c
O
Synthesis of compounds 1a, 1b and 1c: A mixture of
(0.5 mmol), imide (0.55 mmol), NaI (2.5 mmol) in 50
Scheme 1 Synthetic route of 1a-c
5
ml dry DMF was heated under nitrogen with an oil bath
at 85 °C over night with magnetic stirring. The solvent
was removed under reduced pressure and the residue
was purified by column chromatography packed with
silica gel using dichloromethane as eluent to afford pure
product as a yellow solid.
3
.2. Photophysical Properties
The UV-Vis absorption and fluorescence spectra of
1
a-c in CH Cl solution and drop-cast thin films are
2 2
shown in Figures 2-4, and the data are collected in Table
. 1a-c had very similar UV/Vis absorption and
fluorescence spectra in CH Cl , which indicated that the
1
1
Compound 1a: White solid. Yield: 0.12mg, 80%. H
2
2
different alkyl substituents at the nitrogen atom had no
influence on the optical properties of 1a-c. They
displayed well-resolved absorption spectra with maxima
at λ = 363, 363 and 364 nm with molar extinction
coefficients (ε) of 7800, 9200 and 11500 M cm ,
respectively. These absorption spectra of 1a-c were
red-shifted by about 100 nm compared with the
NMR (400 MHz, CDCl ) δ 8.58 (s, 2H), 8.47 (s, 2H),
3
3
.80 (t, J = 4.0 Hz, 2H), 1.73 – 1.70 (m, 2H), 1.42-1.33
13
(m 2H), 0.97 (t, J = 4.0 Hz, 3H). C NMR (100 MHz,
cdcl ) δ 166.2, 137.2, 135.6, 132.0, 124.5, 114.8, 113.4,
3
-1
-1
3
8.5, 30.1, 19.9, 13.6. EI-MS m/z = 303.10. calculated
exact mass = 303.01
Compound 1b: White solid. Yield: 0.15mg, 85%. H
1
spectrum of precursor II (R = n-C H ) because of the
NMR (600 MHz, cdcl ) δ 8.58 (s, 2H), 8.47 (s, 2H),
4
9
3
introducing cyano groups which expand the molecular
conjugation. While the absorption spectra in film state
of 1a-c exhibited a small bathochromic shift compared
3
4
.79 (t, J = 6 Hz, 2H), 1.74-1.70 (m,2H), 1.36-1.32 (m,
H), 1.29 – 1.26 (m, 6H), 0.87 (t, J = 6 Hz, 3H). C
13
NMR (100 MHz, CDCl ) δ 166.2, 137.2, 135.6, 132.0,
3
with that in CH Cl solution. Photoluminescence spectra
1
1
3
24.3, 114.9, 112.8, 38.8, 31.5, 29.0, 28.3, 26.7, 22.5,
3.9. EI-MS m/z = 359.07. calculated exact mass =
2
2
of 1a-c in solution were recorded under excitation at λ =
46 nm and showed the emission maximum at 408, 408
3
59.16
1
and 409 nm, respectively. In the thin film state, the
photoluminescence spectra of 1a-c exhibited broad and
red shifted emission band centered at 482, 487 and 465
nm relative to those in solution, implying the existence
Compound 1c: White solid. Yield: 0.11 mg, 70% H
NMR (400 MHz, cdcl ) δ 8.57 (s, 2H), 8.45 (s, 2H),
3
4
2
.20-4.12 (m,1H), 2.14-2.06 (m, 2H), 1.90 – 1.83 (m,
13
H), 0.90 (t, J = 8 Hz, 3H). C NMR (100 MHz, CDCl )
3
[16]
of strong aggregation in the solid state.
It is worth
δ 166.5, 137.8, 135.3, 131.4, 124.4, 115.8, 111.6, 29.8,
9.6, 13.5. EI-MS m/z = 317.17. calculated exact mass
317.11
noting that the luminescence spectra of compound 1c in
the film-state shifted much less to the long wavelength
compared with those of 1a and 1b, which may due to the
branched alkyl chain R = CH(C H ) in 1c causing a
1
=
2
5 2
Results and discussion
more steric hindrance to aggregation than the straight
alkyl chain R = n-C , n-C 17 in 1a and 1b. The
3
.1. Synthesis
4
H
9
H
8
optical energy gaps (E ) of II and 1a-c were calculated
g
As outlined in Scheme 1, the target molecules 1a-c
from the low-energy absorption onset in the absorption
spectra in solution, as shown in table 1. 1a-c had almost
the same energy gaps which were 0.6 eV smaller than
that of II.
were synthesized in four steps using commercially
available o-xylene 2 as starting material. o-Xylene 2
underwent bromination with bromine and iodine to
[12]
afford 3 in 90% yield.
This was followed by
substitution reaction with CuCN to obtain 4 in 75%
[
13]
yield.
Subsequently, the key intermediate 5 was
[14, 11a]
prepared according to the reported procedure
and
then the Diels-Alder cycloaddition with maleimide
containing different alkyl chains was performed to yield
[15]
compounds 1a-c in high yield. Compounds 1a-c had
good solubility in normal organic solvents such as
2

ACCEPTED MANUSCRIPT
UV-Vis (Solution)
UV-Vis (Solution)
UV-Vis (Film))
PL (Solution)
PL (Film)
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
UV-Vis (Film)
PL (Solution)
PL (Film)
)
1.0
0.8
0.6
0.4
0.2
0.0
3
50
400
450
500
550
600
350
400
450
500
550
600
Wavelength / nm
Wavelength / nm
Figure 2 Normalized UV−vis absorption and photoluminescence
Figure 4 Normalized UV−vis absorption and photoluminescence
−5
−5
spectra of 1a in CH Cl (1.0 × 10 M) and in thin film
spectra of 1c in CH Cl (1.0 × 10 M) and in thin film.
2
2
2
2
UV-Vis (Solution)
UV-Vis (Film))
PL (Solution)
PL (Film)
1a
1b
1.0
0.8
0.6
0.4
0.2
0.0
1c
3
50
400
450
500
550
600
-2.0
-1.5
-1.0
-0.5
0.0
Wavelength / nm
Potential (V)
Figure 3 Normalized UV−vis absorption and photoluminescence
Figure 5 Cyclic voltammograms of 1a-b in dichloromethane (1
−5
spectra of 1b in CH Cl (1.0 × 10 M) and in thin film.
mM) with 0.1 M Bu NPF as supporting electrolyte, AgCl/Ag as
2
2
4
6
reference electrode, Au disk as working electrode, Pt wire as
counter electrode, and scan rate at 50 mV/s
Table 1: Optical and Electrochemical Data of II and 1a-c
a
a
b
1
onset
c
d
e
λ
Abs
λ
max (PL)
ε
max
E
r
E
r
HOMO
[eV]
LUMO
[eV]
E
g
Comps
-1
-1
[
nm]
[nm]
[M cm ]
[V]
[V]
[eV]
2
2
3
3
3
3
3
3
60 (Solution)
369,388 (Solution)
390 (Film)
f
II
67799
-1.80
-1.78
-6.99
-6.70
-6.69
-6.64
-3.02
-3.37
-3.35
-3.29
3.97
64,282 (Film)
46,363 (Solution)
49,367 (Film)
46,363 (Solution)
47.365 (Film)
47,364(Solution)
50,368 (Film)
367,386,408 (Solution)
396,422,482 (Film)
366,386,408 (Solution)
396,417,487 (Film)
366,386,409 (Solution)
393,415,465 (Film)
1
1
a
7860
9200
-1.44
-1.52
-1.41
-1.49
-1.49
3.33
3.34
3.35
b
1
c
11500
-1.51
a
-5
b
c
The wavelength of absorption and photoluminescence in CH Cl (1.0 × 10 M); The molar extinction coefficient; HOMO energy
2
2
d
onset
e
levels were calculated from the onset of the first oxidation according to equation: HOMO = LUMO-Eg; LUMO = -(4.8 + Er ) eV; E
was calculated from the low-energy absorption onset in the absorption spectra according to equations: E = 1240/λonset
λ (solution)=346 nm, λ (film)=352 nm; reference [13a]
g
17]
[
;
g
f
ex
ex
3
.3. Electrochemical Properties
showed one quasi-reversible reduction at -1.44 V while
b showed an irreversible reduction at -1.52 V, and 1c
1
The electrochemical properties of 1a-c were
displayed one reversible reduction waves at -1.51 V.
The LUMO energy levels of -3.37 eV for 1a, -3.35 eV
for 1b and -3.29 eV for 1c were deduced from the onset
investigated by cyclic voltammetry (CV) in dry CH Cl
2
2
at room temperature (Figure 5), and the data were
collected in Table 1. 1a-c exhibited different
electrochemical behaviors in cyclic voltammograms. 1a
onset
potentials of the first reduction wave (Ered ),
according to the following equation: LUMO=-(4.8 +
3

ACCEPTED MANUSCRIPT
onset
Ered ), where the potentials are calibrated to EFc+/Fc
,
naphthalene unit was observed, which accounts for the
100 nm red-shift wiht respect to their presursor II in
their absorption spectra.
The LUMO energy levels of 1a-c are about 0.3 eV
lower than that of II caused by the introduction of
electron withdrawing dicyano groups. These low-lying
LUMO energy levels made them potential candidates
for n-type OSCs. However, no obvious oxidation waves
were observed upon an anodic scan up to 2.0 V. The
HOMO energy level of 1a-c has thus to be determined
1a HOMO
1a LUMO
from the LUMO level minus the E available from
g
1b HOMO
1c HOMO
1
b LUMO
[17]
absorption spectra as described in Table 1.
.4. Crystal Structure
Besides the photophysical and electrochemical
3
1
c LUMO
properties, molecular structure and solid state packing
of these molecules are also of importance when
considering of their potential application as
semiconductors in electronic devices. Single crystal of
1
a was successfully obtained by slow diffusion of
hexane vapor to the chloroform solution. The
single-crystal structure and three-dimensional packing
of 1a are shown in Figure 6. As depicted (A, B and C),
the five-membered imide ring and the dicyano groups
were coplanar with the naphthalene ring. Figure 6 (D)
Figure 7 Frontier molecular orbital profiles of molecules 1a-c
based on DFT (B3LYP/6-31G*) calculations
Conclusions
…
shows the packing view of 1a: C-H O hydrogen
In
summary,
three
dicyano-substituted
bonding and π-π interactions promoted a “head to tail”
dimer conformation of 1a. The distance between the two
molecules of the dimer is 3.441 Å indicating that they
have strong π-π interactions. However, we were unable
to obtain any single crystals of other two
dicyano-substituted 2,3-naphthalimides suitable for
crystallographic analysis.
2,3-naphthalimide derivatives 1a-c have been facilely
prepared by four-step reactions from the o-xylene. Their
optoelectronic properties have been investigated and
2,3-naphthalimide II was present as a reference. The
obtained compounds 1a-c showed bathochromic shift by
100 nm with respect to that of precursor II because of
the dicyano groups which expand the molecular
conjugation. Moreover, the LUMO energy levels of 1a-c
are about 0.3 eV lower than that of II also caused by the
electron withdrawing dicyano groups.
Acknowledgement
A
B
The authors acknowledge financial support from
National Natural Science Foundation of China
(21676113, 21402057, 21472059, 21272088, 21302043);
Supported by the Ministry-Province Jointly Constructed
Base for State Key Lab-Shenzhen Key Laboratory of
Chemical Biology, Shenzhen; Ministry of Education
and the self-determined research funds of CCNU from
the colleges’basic research and operation of MOE
C
D
Figure 6 Single-crystal structure and packing view of 1a: (A) top
view, (B) side view, (C) dimer, (D) pecking-view in space-fill
type. Hydrogen atoms have been omitted in packing view for
clarity.
(
CCNU16A02004). This work was also financially
supported Natural Science Project of Henan Education
172102210229, 172102210231); Key Scientific
Research Projects of Henan Province (16A150005,
6A430003); Young Scholar Training Program of
(
3
.5. DFT Calculations
1
DFT (B3LYP/6-31G**) calculations of 1a-c were
Henan University of Technology (001170); Research
Foundation for Talented Scholars of Henan University
of Technology (2012BS051, 2014BS007).
then conducted to further understand their geometric
and electronic structures (Figure 7). The frontier
molecular orbital profiles of 1a-c showed that the
naphthalene unit possess the largest HOMO and LUMO
coefficients, while the imide groups contributed large to
the LUMO frontier molecular orobital. Moreover,
electron delocalization between dicyano groups and
References
1
(a) Wen, Y.; Liu, Y.; Adv. Mater. 2010, 22(12), 1331; (b)
Anthony, J. E.; Facchetti, A.; Heeney M.; Marder, S. R. Adv.
4

ACCEPTED MANUSCRIPT
Mater. 2010, 22(34), 3876; (c) Kim, H. N.; Guo, Z.; Zhu, W.;
J.; Chi, C.; Wu, J. Tetrahedron Lett. 2010, 51, 6313; (e)
Okamoto, T.; Suzuki, T.; Tanaka, H.; Hashizume, D.; Matsuo,
Y. Chem. Asian J. 2012, 7, 105; (f) Mohebbi, A. R.; Munoz, C.;
Wudl, F. Org. Lett. 2011, 13, 2560; (g) Huang, J.; Wu, D.; Ge,
H. J.; Liu, S. H.; Yin, J. Chin. Chem. Lett. 2014, 25, 1399; (h)
Chaolumen，H.; Enno，M.; Murata，P.; Wakamiya, P. M. Chem.
Asian J. 2014, 9(11), 3136; (i) Li, Y.; Zhang, G.; Zhang, W.;
Wang, J.; Chen, X.; Liu, Z.; Yan, Y.; Zhao, Y.; Zhang, D.
Chem. Asian J. 2014, 9(11), 3207.
Yoon, J.; Tian, H. Chem. Soc. Rev. 2011, 40(1), 79; (d) Jiang,
W.; Li, Y.; Wang, Z. Chem. Soc. Rev. 2013, 42(14), 6113; (e)
Li, Y. Acc. Chem. Res. 2012, 45(4), 723; (f) Wang, Q.; Ma, D.
Chem. Soc. Rev. 2010, 39, 2387. (g) Simon, D. T.; Gabrielsson,
E. O.; Tybrandt, K.; Berggren, M. Chem Rev, 2016, 116,
1
3009-13041. (h) Rivnay, J.; Inal, S.; Salleo, A.; Owens, R. M.;
Berggren, M.; Malliaras, G. G. Nature Reviews Materials,
018, 3, 17086. (i) Li, X. J.; Pan, F.; Sun, C. K.; Zhang, M.;
2
Wang, Z. W.; Du, J. Q.; Wang, J.; Xiao, M.; Xue, L. W.; Zhang,
Z. G.; Zhang, C. F.; Liu, F.; Li, Y. F. Nat. Commun. 2019. DOI:
7
(a) Li, J.; Chang, J.; Tan, H. S.; Jiang, H.; Chen, X.; Chen, Z.;
Zhang, J.; Wu, J. Chem. Sci. 2012, 3, 846; (b) Chang, J.; Li, L.;
Chang, K. L.; Zhang, J.; Wu, J. RSC Advances, 2013, 3(23),
8721.
Jones, B. A.; Ahrens, M. J.; Yoon, M. H.; Facchetti, A.; Marks,
T. J.; Wasielewski, M. R. Angew. Chem., Int. Ed. 2004, 43(46),
6363.
(a) Chang, J.; Ye, Q.; Huang, K.-W; Zhang, J.; Chen, Z.-K.;
Wu, J.; Chi, C. Org. Lett. 2012, 14, 2964. (b) Ye, Q.; Chang, J.;
Huang, K.-W.; Shi, X.; Wu, J.; Chi, C. Org. Lett. 2013, 15,
1194.
1
0.1038/s41467-019-08508-3. (j) Wu, Z. H.; Sun, W. J.; Tian,
H. H.; Yu, Z. F.; Guo, R. X.; Shao, X. F.; Zhang, H. L. Adv.
Electron. Mater. 2018, 5(2), 1800598.
For selected reviews, see: (a) Anthony, J. E.; Facchetti, A.;
Heeney, M.; Marder, S. R.; Zhan, X. Adv. Mater. 2010, 22(34),
8
9
2
3
4
3
876; (b) Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem.
Rev. 2012, 112, 2208. (c) Shao, J. J.; Wang, G. J.; Wang, K.;
Yang, C. J.; Wang, M. F. Polym. Chem. 2015, 6, 6836–6844.
For selected reviews, see: (a) Gelinck, G.; Heremans, P.;
Nomoto, K.; Anthopoulos, T. D. Adv. Mater. 2010, 22(34),
10 For selected reviews and examples: (a) Wu, X.; Zhu, W.;
Chem. Soc. Rev. 2014, 44(13), 4179; (b) Gale, P.; Caltagirone,
C. Chem. Soc. Rev. 2015, 44(13), 4212; (c) Babu, S. S.;
Praveen, V. K.; Ajayaghosh, A. Chem. Rev. 2014, 114, 1973 ;
(d) Yang, Y.; Zhao, Q.; Feng, W.; Li, F. Chem. Rev. 2013, 113,
192. (e) Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev. 2014, 114,
5511; (f) Mukherjee, S.; Thilagar, P. Chem. Eur. J. 2014, 20,
8012; (g) Qiao, Q.; Zhao, M.; Lang, H.; Mao, D.; Cui, J.; Xu,
Z. RSC Adv. 2014, 4, 25790; (h) Vonlanthen, M.; Finney, N. S.
J. Org. Chem. 2013, 78, 3980; (i) Ventura, B.; Bertocco, A.;
Braga, D.; Catalano, L.; d’Agostino, S.; Grepioni, F.; Taddei,
P.; J. Phys. Chem. C 2014, 118, 18646; (j) Lee, M. H.; Jeon, H.
M.; Han, J. H.; Park, N.; Kang, C.; Sessler, J. L.; Kim, J. S. J.
Am. Chem. Soc. 2014, 136, 8430; (k) Huang, J.; Wu, D.; Ge, H.
J.; Liu, S. H.; Yin, J. Chin. Chem. Lett. 2014, 25, 1399; (l)
Hettiarachchi, S. U.; Prasai, B.; McCarley, R. L. J. Am. Chem.
Soc. 2014, 136, 7575.
3
1
778; (b) Zaumseil, J.; Sirringhaus, H. Chem. Rev. 2007, 107,
296. (c) Sun, H. D.; Gerasimov, J; Berggren, M; Fabiano, S. J.
Mater. Chem. C. 2018, 44(6), 11778-11784
(a) Schmidt, R.; Ling, M. M.; Oh, J. H.; Winkler, M.;
Konemann, M.; Bao, Z. N.; Würthner, F. Adv. Mater. 2007,
1
9(21), 3692; (b) Sakamoto, Y.; Suzuki, T.; Kobayashi, M.;
Gao, Y.; Fukai, Y.; Inoue, Y.; Sato, F.; Tokito, S. J. Am. Chem.
Soc. 2004, 126, 8138. (c) S. Holliday, J. E. Donaghey and I.
McCulloch, Chem. Mater., 2014, 26, 647-663. (d) J. T. E.
Quinn, J. Zhu, X. Li, J. Wang and Y. Li, Journal of Materials
Chemistry C, 2017, 5, 8654-8681. (e) Qin, G. Y.; Ji, L. F.; Fan,
J. X.; Zhang, N. X.; Lin, P. P.; Zhang, S. F; Zou, L. Y.; Ren, A.
M. J. Phys. Chem. A. 2019, DOI: 10.1021/acs.jpca.9b00846; (f)
Wang, H.; Huang, J.; Uddin, M. A.; Liu, B.; Chen, P.; Shi, S.
B.; Tang, Y. M.; Xing, G. C.; Zhang, S. M.; Woo, H. Y.; Guo,
H.; Guo, X. G. Acs Appl. Mater. Interfaces. 2019, DOI:
1
0.1021/acsami.8b22457. (g) Sun, H. L.; Tang, Y. M.; Koh, C.
11 (a) Wu, D.; Zhang, H.; Liu, S. H.; Yin, J. Chem. Asian J. 2015,
10, 602; (b) Wu, D.; Chen, Z.; Zhang, Y. F.; Zhang, J.; Liu, S.
H.; Yin, J. J. Org. Chem. 2015, 80, 8443. (c) Wu, D.; Zhang, Y.
F.; Zhang, J.; Liu, S. H.; Yin, J. Chem. Asian J. 2015, 10,
1344.
12 (a) Chan, S. H.; Yick, C. Y.; Wong, H. N. C. Tetrahedron,
2002, 58(46), 9413. (b) Bose, A.; Mal, P. Tetrahedron, 2014,
55(13), 2154. (c) He, N.; Chen, Y.; Doyle, J.; Liu, Y.; Blau, W.
J. Dyes and Pigments, 2008, 76, 569.
13 (a) Camenzind, M. J.; Hill, C. L.; J. Heterocycl.
Chem, 1985, 22(2), 575. (b) Ivanov,A. V.; K. Kabanova, V.;
Breusova, M. O.; Zhukov, I. V.; Tomilova, L. G.; Zefirovb, N.
S. Russ. Chem. Bull., Int. Ed. 2008, 57(8), 1665-1670.
14 Mataka, S.; Kurisu, M.; Takahashi, K.; Tashiro, M. Chem. Lett.
1984, 13, 1969.
W.; Ling, S. H.; Wang, R. Z; Yang, K.; Yu, J. W.; Shi, Y. Q.;
Wang, Y. F.; Woo, H. Y.; Guo, X. G. Adv. Mater. 2019, 31 (15),
1
(a) Li, Y.; Tan, L.; Wang, Z.; Qian, H.; Shi, Y.; Hu, W. Org.
Lett. 2008, 10(4), 529; (b) Lei, T.; Dou, J. H.; Ma, Z. J.; Yao,
C. H.; Liu, C. J.; Wang, J. Y.; Pei, J. J. Am. Chem. Soc. 2012,
807220.
5
1
34(49), 20025; (c) Schmidt, R.; Oh, J. H.; Sun, Y. S.;
Deppisch, M.; Krause, A. M.; Radacki, K.; Braunschweig, H.;
Könemann, M.; Erk, P.; Bao, Z.; Würthner, F. J. Am. Chem.
Soc. 2009, 131(131), 6215; (d) Jones, B. A.; Facchetti, A.;
Wasielewski, M. R.; Marks, T. J. J. Am. Chem. Soc. 2007,
1
29(49), 15259. (e) Peltier, J. D.; Heinrich, B.; Donnio, B.;
Jeannin, O.; Rault-Berthelot, J .; Jacques, E.; Poriel, C. J.
Mater. Chem. C. 2018, 6, 13197-13210.
6
For selected examples, see: (a) Qu, H.; Cui, W.; Li, J.; Shao, J.; 15 (a) Beare, K. D.; Yuen, A. K. L.; Masters, A. F.; Maschmeyer,
Chi, C. Org. Lett. 2011, 13, 924; (b) Katsuta, S.; Tanaka, K.;
Maruya, Y.; Mori, S.; Masuo, S.; Okujima, T.; Uno, H.;
Nakayama, K.; Yamada, H. Chem. Commun. 2011, 47, 10112;
T.; McErlean, C. S. P. Chem. Commun. 2013, 49, 8347; (b) Li,
K.; Yuan, C.; Zheng, S.; Fang, Q. Tetrahedron Lett. 2012, 53,
4245; (c) Coleman, L.; Bork, J.; Dunn, H. J. Org. Chem. 1959,
24, 135; (d) Barros, T. C. de; Filho, P. B.; Loos, M.; Politi, M.
J.; Chaimovich, H.; Cuccovia, I. M. J. Phys. Org. Chem. 2011,
(c) Yin, J.; Qu, H.; Zhang, K.; Luo, J.; Zhang, X.; Chi, C.; Wu,
J. Org. Lett. 2009, 11, 3028; (d) Yin, J.; Zhang, K.; Jiao, C.; Li,
5

ACCEPTED MANUSCRIPT
2
4, 385; (e) Yin, J.; Qu, H.; Zhang, K.; Luo, J. Zhang. X.; Chi,
S. H.; Yin, J.; J. Org. Chem. 2012, 77, 11319;; (e) Hu, Y.;
C.; J. Wu, Org. let. 2009, 11, 3028.
Wang, Z. L.; Yang, X.; Zhao, Z.; Han, W.; Yuan, W.; Li, H.;
Gao, X.; Zhu, D. Tetrahedron Lett. 2013, 54, 2271.
17 Chi, C.; Wegner, G.; Macromol. Rapid Commun. 2005, 26,
1532.
1
6
(a) Jelley, E. E. Nature. 1936, 138, 1009; (b) E. E. Jelley,
Nature. 1937, 139, 631-632; (c) Daltrozzo, E.; Scheibe, G.;
Geschwind, K.; Haimerl, F. Photogr. Sci. Eng. 1974, 18, 441;
(d) Wu, D.; Zhang, H.; Liang, J.; Ge, H.; Chi, C.; Wu, J.; Liu,
6

ACCEPTED MANUSCRIPT
FULL PAPER
Graphical Stract
*
E-mail: jinling_li@haut.edu.cn; yinj@mail.ccnu.edu.cn; Tel.: +86-0371-67758722; Fax: +86-27-67867725
Received ((will be filled in by the editorial staff)); revised ((will be filled in by the editorial staff)); accepted ((will be filled in by the editorial staff)).
Supporting information for this article is available from the author.

ACCEPTED MANUSCRIPT
Highlights
ò
ò
ò
ò
2,3-naphthalimide has been cyanated by a short synthesis route.
Dicyano-substituted 2,3-Naphthalimide has a large bathochromic shift.
Dicyano-substituted 2,3-Naphthalimide possesses a low-lying LUMO energy level.
The crystal packing appears conducive for effective charge transport.