Dyes and Pigments 163 (2019) 615–622

Contents lists available at ScienceDirect

Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Nitrogen-embedded small-molecule semiconducting materials: Effect of T

chlorine atoms on their electrochemical, self-assembly, and carrier transport
properties
Yankai Zhoua,b,1, Zuzhang Lina,1, Xiaotong Liub, Hao Lia, Weifeng Zhangb,∗∗, Liping Wanga,∗,
Gui Yub,c,∗∗∗
a
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, PR China
b
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of
Sciences, Beijing, 100190, PR China
c
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, PR China

ARTICLE INFO ABSTRACT

Keywords: We reported three novel nitrogen-embedded small molecules 4a, 4b, and 4c, which were synthesized from the
Small-molecule semiconductors condensation reactions of benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione with 1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]
Organic field-effect transistors pyridine-2,3-dione, 6-chloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione, or 4,6-dichloro-1-(2-ethyl-
Electron mobilities hexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione, respectively. Their optical, electrochemical properties, self-as-
Isoindigo derivatives
sembly behavior, and carrier transport properties were studied by a range of experimental and theoretical
Chlorine atoms
methods, and the effect of chlorine atoms were well discussed. Energy levels of the highest occupied molecular
orbitals and the lowest unoccupied ones for these molecular materials locate at −5.92∼−6.02 and
−4.25∼−4.37 eV, respectively. Bottom gate/bottom contact field-effect transistors based on 4a, 4b, and 4c
exhibited typical n-channel transport characteristics with the highest electron mobility of
7.57 × 10−3 cm2 V−1 s−1. Thin film microstructure investigations revealed 4a and 4c perform lamellar mole-
cular packing with random orientations to the OTS-treated SiO2 substrate, while 4b conducts a highly crystal-
line, edge-on, lamellar packing though large grain boundaries exist in its thin film.

1. Introduction
Compared with the traditional silicon-based semiconducting mate-
rials, organic semiconducting materials have several advantages: firstly,
their physicochemical properties are more regulatable, thus a great
variety of organic semiconducting materials with various thermal, op-
tical, electrochemical properties could be simply obtained by modifying
the conjugated structures of molecules, even only by changing their
alkylated side chains [1–3]. Secondly, organic semiconducting mate-
rials possess better elasticity and flexibility, leading to better compat-
ibility with flexible substrates and great potentials in flexible electro-
nics devices [4,5]. Most of these materials are solution processable,
providing much convenience for the manufacture of large area elec-
tronic devices with low-cost [6,7]. As a result, organic semiconducting
materials have garnered much attention from both academia and in-
dustry, and great achievements have been acquired in organic field-
effect transistors (OFETs) and organic photovoltaic cells under the joint
efforts of scientists from multiple disciplines during the recent decades
[8,9]. For example, far exceeding the performance of amorphous silicon
(∼0.1–1.0 cm2 V−1 s−1) has been witnessed in many OFETs based well-
designed small molecules and donor−acceptor (D−A) copolymers
[10,11]. Nevertheless, there is still a long way to go before these OFETs
are widely used in the next generation electronic devices such as flex-
ible RFID tags, sensors, large-screen displays and integrated circuits.
One of the difficulties is that the performance and air-stability of cur-
rent n-channel OFET devices are still unsatisfied. In this regard, the
exploring of new n-type semiconducting materials with diversity
structures is challenging and rewarding.

Corresponding author.
∗

Corresponding author.
∗∗

Corresponding author. Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of
∗∗∗

Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR China.

E-mail addresses: zhangwf@iccas.ac.cn (W. Zhang), lpwang@mater.ustb.edu.cn (L. Wang), yugui@iccas.ac.cn (G. Yu).
1
Authors Y. Zhou and Z. Lin contributed equally to this work.

https://doi.org/10.1016/j.dyepig.2018.12.051
Received 3 September 2018; Received in revised form 19 December 2018; Accepted 22 December 2018
Available online 24 December 2018
0143-7208/ © 2018 Elsevier Ltd. All rights reserved.
Y. Zhou et al.
In order to obtain n-type semiconducting materials, the adjustment of
their lowest unoccupied molecular orbital (LUMO) energy levels to facil-
itate electron injection and the formation of high-ordered thin film are
necessary. The generally accepted suitable LUMO energy levels should be
located at −4.0 eV or lower [12]. At present, several methods are com-
monly used to achieve this goal. Among them, developing novel electron-
deficient aromatics is being widely used. Beside naphthalimide (NDI), [13]
diketopyrropyrroles (DPP), [14] and isoindigo (IID), [15] novel 7,15-dia-
zadiazuleno[1,2,3-ef:1′,2′,3′-kl]heptalene-6,8,14,16(7H,15H)-tetraone
(TBAzDI), [16] 2,2ꞌ-bithiazolothienyl-4,4ꞌ,10,10ꞌ-tetracarboxydiimide
(DTzTI), [17] and (3E,7E)-3,7-bis(2-oxo-1H-pyrrolo[2,3-b]pyridin-3(2H)-
ylidene)benzo[1,2-b:4,5-b′]difuran-2,6(3H,7H)-dione (NBDO) had been
recently designed and synthesized, exhibiting advantageous potential in
constructing high performance electron-mobility semiconducting mate-
rials [18,19]. Note that the lactam groups contained in above-mentioned
aromatics could efficiently lower the LUMO energy levels of semi-
conducting materials and make it possible to vary chain lengths and push
the branching point away from the conjugated backbone, which have
important influence on molecular packing mode and intra-/interchain
carrier transport [20]. On the other hand, the incorporation of heteroatom
atoms and groups, for example F, Cl, and cyano group, etc. onto aromatic
skeletons is also one versatile approach in tuning the molecular packing
mode in solid state though no apparent influences were found on the
frontier orbital energy levels [21–23]. For small-molecule semiconductors,
especially acene-like small-molecule semiconductors, the progressive
chlorine substitution is much useful [24]. For example, both 6,13-di-
chloropentacene and 5,6,11,12-tetrachloronaphthacene exhibited im-
proved molecular packing in solid state, thus leading to high charge carrier
transport properties and air-stabilities. Several representative chlorinated
small-molecule semiconductors and their charge transport performance
are collected in Table S1. Nevertheless, most of them showed p-type
charge transport properties and their high mobilities were always obtained
in singe crystal FET devices.
In this work, we reported three novel nitrogen-embedded small
molecules 4a, 4b, and 4c (Scheme 1), which were synthesized from the
condensation reactions of benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione
with 1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione, or 6-
chloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione, and 4,6-
dichloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione, respec-
tively. The optical and electrochemical properties of the three small-
molecule materials were examined by UV−vis absorption and cyclic
voltammetry (CV), respectively. Their thin film microstructures were
Scheme 1. Synthetic routes of nitrogen-embedded small-molecular materials 4a, 4b, and 4c.
616
Dyes and Pigments 163 (2019) 615–622
investigated by atomic force microscopy (AFM) in tapping mode and
two-dimensional grazing incidence X-ray diffraction (2D-GIXRD). The
charge transport properties of these molecular materials were evaluated
by fabricating thin film field-effect transistors with bottom gate/bottom
contact (BG/BC) device configuration on octadecyltrichlorosilane
(OTS)-modified SiO2 substrates. Meanwhile, the effect of chlorine
atoms on the optoelectronic properties for the three molecular mate-
rials were well discussed.
2. Experimental section
2.1. Materials and characterizations
The chemical reagents and solvents including N,N-dimethylaceta-
mide (DMF), sodium hydride, pyridine chlorochromate, aluminum
trichloride, p-toluenesulfonic acid, and 3-(bromomethyl)heptane were
purchased from Sinopharm, Acros, Alfa, and Sigma-Aldrich and used
without further purification. Benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-
dione was synthesized according to the method reported in the reported
literature. All oxygen- and water-sensitive reaction were carried out
using the Schlenk technique in an argon or nitrogen atmosphere with
anhydrous solvents.
1
H NMR and 13C NMR spectra of intermediates were recorded on a
Bruker Fourier 300/400/500 NMR spectrometer (Bruker Daltonics,
German) with chemical shifts referenced to TMS (0 ppm). High re-
solution mass spectroscopy (HRMS) measurements were performed on
a Bruker Biflex III mass spectrometer (Bruker Daltonics, Billerica, MA,
USA) or a Bruker 9.4T Solarix mass spectrometer (Bruker Daltonics,
Billerica, MA, USA). Elemental analyses were carried out on a Carlo
Erba 1106 Elemental Analyzer (Carlo-Erba, Italy). UV−vis absorption
spectra were recorded on a U-3010 spectrophotometer (Hitachi, Japan),
photoluminescent (PL) spectra were recorded on a Jasco FP-6000
spectrometer (Jasco, Japan), and infra-red (IR) spectra were recorded
on a Bruker TENSOR-27 spectrometer (Bruker Daltonics, German) at
room temperature. Cyclic voltammetry (CV) curves measurements were
collected on a CHI660c electrochemistry workstation (Shanghai, China)
using 0.1 M n-Bu4NPF6, platinum stick electrode, Ag/AgCl electrode,
and platinum wire as supporting electrolyte, working electrode, re-
ference electrode, and counter electrode, respectively. Density func-
tional theory (DFT) calculations were performed at the B3LYP/6-31G*
levels with the Gaussian 03, Revision C. 02 package. Thin film
morphologies of these polymer materials were investigated on a Digital
Y. Zhou et al. Dyes and Pigments 163 (2019) 615–622

Fig. 1. Normalized UV-Vis absorption spectra of nitrogen-embedded small-molecular materials 4a, 4b, and 4c, in chloroform solution (a) and thin film coated on
quartz plates (b).

Table 1
Optical and electrochemical properties of three nitrogen-embedded small-mo-
lecule materials.
polymer λmax (nm) Egopt (eV)c ox
Eonset (V)d red
Eonset (V)d EHOMO ELUMO
(eV)d (eV)d

4a 571a/574b 1.50 1.52 −0.15 −5.92 −4.25

4b 580a/596b 1.50 1.55 −0.04 −5.95 −4.36
4c 613a/600b 1.65 1.62 −0.03 −6.02 −4.37

a
In chloroform solution.
b
Thin film.
c
Calculated from the absorption edges (Egopt = 1240/ edge ).
abs

d
Determined by CV.

Instruments Nanoscope V atomic force microscope (Digital Instruments,

USA) operated in tapping mode. 2D-GIXRD data were studied by illu-
minating the thin film samples at a constant incidence angle of 0.2°
(Beamline BL14B1 of the Shanghai Synchrotron Radiation Facility).

2.2. General procedures for OFETs fabrication and measurements
OFET devices with bottom-gate/bottom-contact (BGBC) configura-
tions were fabricated on heavily doped silicon wafers covered with
300 nm thick silicon dioxide layers. Gold (Au) source/drain electrodes
were prepared by photolithography technique. The substrates were fully
cleaned by ultrasonication in acetone, deionized H2O, and ethanol (5 min
for each solvent) and subsequently dried under vacuum at 80 °C for
30 min, then treated with octadecyltrichlorosilane (OTS) to form an OTS
self-assembled monolayer on the surface of silica substrates.
Semiconducting layers were deposited on the OTS-treated substrate by
spin-coating a small molecule solution (10 mg/mL) in o-dichlorobenzene
at 3000 rpm for 60 s and annealed on a hot plate at 80–200 °C at an
interval of 40 °C for 5 min. After cooling the devices to the r.t., the device
fabrication process was completed. Both the fabricating and measuring
processes were conducted in a glovebox. The evaluations of FET devices
were performed on a Keithley 4200 SCS semiconductor parameter ana-
lyzer on a probe stage. The carrier mobility, μ, was calculated from the
data in the saturated regime according to the equation:
W roleum ether/dichloromethane (8:1) as eluent affording the desired
IDS = Ci µ(VG VT )2
2L
where IDS is the saturation drain current, W/L is the channel width/
length, Ci is the capacitance per unit area of the gate dielectric layer, and
Fig. 2. CV traces of nitrogen-embedded small-molecule materials 4a, 4b, and
4c.
VG and VT are the gate voltage and threshold voltage, respectively. The
channel lengths (L) and channel width (W) of the FET devices in this
study are 50 and 1400 μm, respectively.
2.3. Synthetic procedures
2.3.1. Synthesis of 1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine, 2a
To a solution of 1 (5.00 g, 42.3 mmol) in anhydrous DMF (70 mL)
was added sodium hydride (2.03 g, 50.8 mmol) slowly under ice bath
for half an hour. The mixture was stirred at r.t over night after 3-
(bromomethyl)-hexane (10.6 g, 55.0 mmol) was then injected into the
solution. The reaction was quenched by water until no obvious bubble
generating. The reaction mixture was extracted with ethyl acetate and
dried over anhydrous sodium sulfate. After removing the solvent, the
residue was purified by silica gel column chromatography using pet-
product as the colorless liquid (8.29 g, 85%). 1H NMR (300 MHz,
CDCl3) δ 8.24 (d, J = 4.7 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.11 (d,
J = 3.4 Hz, 1H), 6.95 (dd, J = 7.8, 4.7 Hz, 1H), 6.36 (d, J = 3.4 Hz,
1H), 4.11 (d, J = 7.4 Hz, 2H), 1.95–1.80 (m, 1H), 1.20 (s, 8H), 0.78

617
Y. Zhou et al. Dyes and Pigments 163 (2019) 615–622

Fig. 3. Predicted frontier molecular orbital distributions of nitrogen-embedded small-molecular materials 4a (a), 4b (b), and 4c (c).

Table 2 23.83, 23.01, 14.03, 10.71. HR-MS (MALDI-TOF) m/z: Calcd for
BGBC FET device performance of nitrogen-embedded small-molecular mate- C15H21N2Cl: 264.1393. Found: 264.1466.
rials.
Materials μe (cm2 V−1 s−1) Vth (v) Ion/Ioff 2.3.3. Synthesis of 4,6-dichloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]
pyridine, 2c
Maxa Aveb The synthetic procedure of 2c is similar to that of 2a (3.70 g, 85%).
1
4a 5.17 × 10−3 3.90 × 10−3 −15–1 102∼103
H NMR (300 MHz, CDCl3) δ 7.17 (d, J = 3.5 Hz, 1H), 7.09 (s, 1H), 6.52
4b 7.13 × 10−3 4.24 × 10−3 −10∼−1 102∼103 (d, J = 3.5 Hz, 1H), 4.12 (d, J = 7.2 Hz, 2H), 1.95–1.79 (m, 1H),
4c 7.57 × 10−3 6.56 × 10−3 −1–11 102∼103 1.37–1.09 (m, 9H), 0.86 (dt, J = 6.9, 5.5 Hz, 7H). 13C NMR (75 MHz,
CDCl3) δ 147.00, 144.26, 130.81, 128.43, 118.79, 115.53, 99.70,
a
The maximum electron mobilities. 47.95, 40.13, 30.43, 28.47, 23.83, 23.01, 14.03, 10.59. HR-MS
b
The average values were calculated from more than 10 devices.
(MALDI-TOF) m/z: Calcd for C15H20N2Cl2: 298.1004. Found: 298.1078.

(dd, J = 19.2, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 147.97,
142.61, 128.22, 128.09, 120.17, 115.26, 99.21, 47.93, 40.06, 30.46,
28.47, 23.80, 22.78, 13.94, 10.47. HRMS (MALDI-TOF) m/z: Calcd for
C15H22N2: 230.1783. Found: 230.2013.
2.3.2. Synthesis of 6-chloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine,
2b
The synthetic procedure of 2b is similar to that of 2a (6.50 g, 88%).
1
H NMR (300 MHz, CDCl3) δ 7.81 (d, J = 8.1 Hz, 1H), 7.16 (d,
J = 3.5 Hz, 1H), 7.04 (d, J = 8.1 Hz, 1H), 6.44 (d, J = 3.5 Hz, 1H), 4.15
(d, J = 7.3 Hz, 2H), 2.01–1.83 (m, 1H), 1.38–1.08 (m, 8H), 0.87 (dt,
J = 9.8, 6 Hz, 7H). 13C NMR (100 MHz, CDCl3) δ 147.00, 144.26,
130.81, 128.43, 118.79, 115.53, 99.70, 47.95, 40.13, 30.58, 28.47,
2.3.4. Synthesis of 1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-2,3-dione,
3a
To a suspension containing pyridinium chloride (6.55 g,
30.4 mmol), silica gel (6.55 g) and 1,2-dichloroethane (60 mL) was
added 2a (2.00 g, 8.68 mmol). The mixture was stirred at r.t for 15 min,
after which 10 mg AlCl3 was added in one portion. The reaction mix-
tures were refluxed for 3 h and then cooled down to the r.t. After re-
moving the solvent, the residue was purified by silica gel column
chromatography using petroleum ether/dichloromethane (3:1) as
eluent affording the desired product as a yellow solid (1.70 g, 75%). 1H
NMR (300 MHz, CDCl3) δ 8.44 (dd, J = 5.2, 1.8 Hz, 1H), 7.81 (dd,
J = 7.4, 1.8 Hz, 1H), 7.06 (dd, J = 7.4, 5.2 Hz, 1H), 3.74 (d, J = 7.3 Hz,
2H), 1.99 (m, 1H), 1.36–1.31 (m, J = 4.6 Hz, 8H), 0.97–0.76 (m, 6H).

Fig. 4. Output (a) and transfer (b) characteristics of 4c-based OFETs on OTS-modified SiO2/Si substrate (W = 1500 μm, L = 50 μm; Annealed at 120 °C).

618
Y. Zhou et al. Dyes and Pigments 163 (2019) 615–622

Fig. 5. Thin-film AFM images and 2D-GIXRD patterns of nitrogen-embedded small-molecular materials 4a, 4b, and 4c after annealing at their respective optimal
temperatures.

13
C NMR (100 MHz, CDCl3) δ 182.22, 164.45, 158.61, 155.88, 132.65, 1.97–1.84 (m, 1H), 1.43–1.19 (m, 8H), 1.01–0.76 (m, 6H). 13C NMR
119.32, 111.95, 43.33, 37.32, 30.45, 28.40, 23.83, 23.00, 14.02, 10.38. (75 MHz, CDCl3) δ 147.00, 144.26, 130.81, 128.43, 118.79, 115.53,
HRMS (MALDI-TOF) m/z: Calcd for C15H20N2O2: 260.1525. Found: 99.70, 47.95, 40.13, 30.43, 28.47, 23.83, 23.01, 14.03, 10.59. HRMS
260.1598. (MALDI-TOF) m/z: Calcd for C15H18N2O2Cl2: 328.0745. Found:
328.0639.
2.3.5. Synthesis of 6-chloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b]pyridine-
2,3-dione, 3b
2.3.7. Synthesis of 4a
The synthetic procedure of 3b is similar to that of 3a (2.30 g, 71%).
1 To a solution of benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione
H NMR (300 MHz, CDCl3) δ 7.75 (d, J = 7.8 Hz, 1H), 7.08 (d,
(264 mg, 3.46 mmol) and p-toluenesulfonic acid (76.1 mg, 0.400 mmol)
J = 7.8 Hz, 1H), 3.72 (d, J = 7.3 Hz, 2H), 2.03–1.83 (m, 1H), 1.36 (m,
in acetic acid (30 mL) was added 3a (900 mg, 3.46 mmol). The resulting
8H), 0.91 (m, 6H). 13C NMR (75 MHz, CDCl3) δ 180.53, 164.99, 158.93,
mixture was heated to reflux and stirred for 12 h. Then the reaction
158.52, 134.52, 119.29, 110.08, 43.42, 37.38, 30.41, 28.29, 23.86,
mixture was cooled to r.t, the crude product was obtained by filtration.
22.98, 14.05, 10.39. HRMS (MALDI-TOF) m/z: Calcd for C15H19N2O2Cl:
After being washed with water and extracted by chloroform, the residue
294.1135. Found: 294.1209.
was purified by silica gel column chromatography using petroleum
ether/dichloromethane (1:1) as eluent affording the desired product as
2.3.6. Synthesis of 4,6-dichloro-1-(2-ethylhexyl)-1H-pyrrolo[2,3-b] a solid (489 mg, 52%). 1H NMR (300 MHz, CDCl3) δ 8.44 (dd, J = 5.2,
pyridine-2,3-dione, 3c 1.8 Hz, 1H), 7.81 (dd, J = 7.4, 1.8 Hz, 1H), 7.06 (dd, J = 7.4, 5.2 Hz,
The synthetic procedure of 3c is similar to that of 3a (2.60 g, 67%). 1H), 3.74 (d, J = 7.3 Hz, 2H), 1.99 (s, 1H), 1.31 (d, J = 4.6 Hz, 8H),
1
H NMR (300 MHz, CDCl3) δ 7.04 (s, 1H), 3.71 (d, J = 7.3 Hz, 2H), 0.97–0.76 (m, 6H). 13C NMR (125 MHz, d2-CDCl2CDCl2) δ 167.10,

619
Y. Zhou et al.
166.90, 159.19, 152.22, 151.73, 137.23, 135.23, 127.19, 126.93,
118.49, 115.63, 111.26, 43.82, 37.80, 31.02, 28.68, 24.44, 22.94,
13.85, 10.67. HRMS (MALDI-TOF) m/z: Calcd for C40H42N4O6:
674.3104. Found: 674.2997. Elemental Anal. Calcd for C40H42N4O6: C,
71.20; H, 6.27; N, 8.30; Found: C 70.94, H 6.29, N 8.20.
2.3.8. Synthesis of 4b
The synthetic procedure of 4b is similar to that of 4a (288 mg,
49%). 1H NMR (500 MHz, d2-CDCl2CDCl2) δ 9.18 (d, J = 8.3 Hz, 1H),
9.14 (s, 1H), 7.05 (d, J = 8.3 Hz, 1H), 3.83 (dd, J = 7.1, 2.3 Hz, 2H),
2.09–1.92 (m, 1H), 1.61–1.16 (m, 8H), 0.96 (m, 7.3 Hz, 6H). 13C NMR
(125 MHz, d2-CDCl2CDCl2) δ 167.10, 166.84, 159.33, 154.46, 152.36,
139.16, 133.87, 127.25, 126.99, 118.17, 113.81, 111.28, 43.94, 37.88,
30.99, 28.59, 24.45, 22.90, 13.84, 10.62. HRMS (MALDI-TOF) m/z:
Calcd for C40H40N4O6Cl2: 742.2325. Found: 742.2398. Elemental Anal.
Calcd for C40H40Cl2N4O6: C, 64.60; H, 5.42; N, 7.53; Found: C 64.98, H
5.61, N 7.02.
2.3.9. Synthesis of 4c
The synthetic procedure of 4c is similar to that of 4a (52.6 mg,
15%). 1H NMR (300 MHz, CDCl3) δ 8.71 (s, 1H), 7.07 (s, 1H), 3.75 (d,
J = 7.2 Hz, 2H), 1.98–1.89 (m, 1H), 1.37–1.22 (m, 8H), 0.98–0.79 (m,
6H). 13C NMR (125 MHz, d2-CDCl2CDCl2) δ 167.28, 164.49, 160.29,
153.87, 152.54, 145.30, 132.00, 131.64, 128.49, 119.66, 113.53,
111.25, 44.54, 38.25, 31.17, 28.78, 24.63, 23.01, 13.95, 10.73. HRMS
(MALDI-TOF) m/z: Calcd for C40H38N4O6Cl4: 810.1545. Found:
810.1619. C, 64.60; H, 5.42; Cl, 9.53; N, 7.53; Elemental Anal. Calcd for
C40H38Cl4N4O6: C, 59.12; H, 4.71; N, 6.90; Found: C 59.60, H 4.69, N
6.57.
3. Results and discussion
3.1. Synthesis
The synthetic routes of the three nitrogen-embedded small-molecule
materials, 4a, 4b, and 4c are shown in Scheme 1. The compounds
2a−2c were synthesized by the alkylation reactions of compound
1a−1c in high yield, respectively. Then the compound 2a−2c reacted
with pyridinium chloride (PCC) in the presence of AlCl3 affording the
respective oxidation products 3a−3c. In the preliminary try (with 1.0
eq. PCC to 3a), the yield of 3a is low down to 25% due to the dimer-
ization of 2a. However, the yield dramatically improved to 75% when
the eq. of PCC increased to three times of 2a. Aldol condensation re-
action of 3a, 3b, or 3c with benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-
dione gave the target organic small-molecule materials 4a, 4b, and 4c,
respectively. Note that the yields of 4a and 4b were around 50%,
whereas the field of 4c was only 15%. This might be originated from its
larger steric hindrance of 4c than those of 4a and 4b.
3.2. Photophysical properties
The photophysical properties of the three small molecules were
investigated by characterizing their UV-Vis absorption spectra (Fig. 1),
infra-red (IR) spectra (Fig. S1), and photoluminescent (PL) spectra (Fig.
S2). The UV-Vis absorption spectra of the three small molecules were
recorded in chloroform solutions and as-spun thin films coated on
quartz plates. All these small molecules exhibited typical dual-band
absorption at 350–450 and 470–700 nm both in solution and thin film.
In solutions, the maximum absorption peaks ( max abs
) of 4a, 4b, and 4c
locate at 571, 580 and 613 nm, respectively (Table 1). The red-shifted
absorption spectra from 4a, 4b, to 4c could be attributed to the in-
troduction and the number increase of chlorine atoms. Note the thin
films of these molecules have distinct different absorption spectra
compared to those in solutions. Firstly, the max abs
of 4a and 4b red-
shifted to 574 and 596 nm, respectively, whereas the max abs
of 4c blue-
shifted to 600. Secondly, the absorption edges ( edge ) of 4a and 4b
abs
620
Dyes and Pigments 163 (2019) 615–622
locate at ca. 800 nm while the edgeabs
of 4c locates is ca. 750 nm. This
indicates that more effective aggregation or orderly π−π stacking oc-
curs in the solid state films of 4a and 4b than 4c, which might be as-
cribed to their different molecular conjugated backbone conformations
and intermolecular interactions induced by the incorporation of
chlorine atoms [25]. Based on the edge
abs
, the optical bandgap (Egopt ) of 4a,
4b, and 4c was estimated to be 1.50, 1.50, and 1.65 eV, respectively. In
addition, a weak PL emission was obtained in the 4b solution (Fig. S2),
whereas no PL emissions were found in the 4a and 4c solutions.
3.3. Electrochemical properties
The electrochemical properties of three small molecules were
measured by cyclic voltammetry (CV) (Fig. 2). All measuring process
was performed in 0.1 M n-Bu4NPF6 solution in anhydrous acetonitrile
under argon atmosphere. The 4a, 4b, or 4c thin film coated on platinum
stick and Ag/AgCl were used as working electrode and reference elec-
trode, respectively. For accuracy, ferrocene (FC) was calibrated as ex-
ternal standard via an Fc/Fc+ couple, whose redox potential had an
absolute value of 4.8 eV vs vacuum. In these conditions, the onset po-
tential of FC was 0.40 V. The Eonset
ox
of 4a, 4b, and 4c are 1.52, 1.55, and
1.62 eV respectively. Thus, the HOMO energy level could be estimated
to be −5.92 eV for 4a, −5.95 eV for 4b, and −6.02 eV for 4c, ac-
cording to the calculation equation, EHOMO = − (Eonset
ox
Eonsetox+4.40)
eV (Table 1). Similarly, based on their respective Eonset red
of −0.15,
−0.04, and −0.03 eV, the LUMO energy levels of 4a, 4b and 4c were
estimated to be −4.25, −4.36, and −4.37 eV, respectively, according
to the calculation equation of ELUMO = − (Eonsetred
+4.40) eV. Therefore,
the energy gap was also calculated as 1.72 eV for 4a, 1.59 eV for 4b and
1.59 eV for 4c. Such results show the HOMO and LUMO energy levels
lowered from 4a, 4b, to 4c, implying that both frontier orbital energy
levels are slightly reduced with the introduction and number increase of
chlorine atoms.
3.4. Theoretical calculations
For well understanding the effect of chlorine atoms on optical and
electrochemical properties of these compounds, hybrid DFT calcula-
tions were performed at B3LYP/6-31G* level, in which the alkyl side
chains were replaced with methyl groups for simplicity. As shown in
Fig. 3, both the HOMOs and the LUMOs are well delocalized along the
conjugated backbone for all the three small molecules. Moreover, mo-
lecules 4a and 4b possess high planar conjugated backbone con-
formations, indicating that the incorporation of chlorine atoms onto the
6-position has little negative effects on the planarity of these molecules.
However, the molecule 4c have a conjugated backbone with a certain
degree of distortion due to the large steric hindrance between the
oxygen atoms of carbonyl and the substituted chlorine atoms at 4-po-
sition. The result could be used to interpret their different molecular
aggregation in thin film as aforementioned. In addition, the predicted
HOMO/LUMO energy levels are −3.64/−6.02 eV for 4a, −3.86/
−6.17 eV for 4b, and −3.99/−6.22 eV for 4c, whose change trend are
consistent with those estimated by electrochemical data.
3.5. Charge carrier transport properties
BGBC OFET devices were fabricated to investigate the charge carrier
transport properties of the three small-molecule materials. The semi-
conducting layer was deposited on the OTS-modified SiO2/Si substrate
by spin-coating the small-molecule solution (10 mg/mL in chloroform).
Then the resulting OFET devices were annealed at 80–200 °C at an in-
terval of 40 °C in nitrogen atmosphere. All the three small-molecule
materials exhibited typical n-type carrier transport characteristics. The
annealing temperature-dependent electron mobilities (μe) were de-
picted in Fig. S3. The optimal annealing temperature is 120 °C for 4a,
80 °C for 4b, and 120 °C for 4c. The maximum electron mobilities of
Y. Zhou et al.
4a-, 4b-, and 4c-based OFET devices were 5.17 × 10−3, 7.13 × 10−3,
and 7.57 × 10−3 cm2 V−1 s−1, respectively (Table 2). The re-
presentative transfer and output characteristics are shown in Figs. S4
and Fig. 4. On the contrary, when these thin films were annealed at the
other temperatures as well as as-spun ones, lower mobilities were af-
forded, which could be originated from the thin film microstructure
changes induced by thermal annealing process.
3.6. Thin-film microstructure analysis
Atomic force microscope (AFM) in tapping mode was used to study
the thin film surface morphology of three small molecules. Fig. 5a−c and
Fig. S5 depict the surface morphologies of 4a, 4b, and 4c thin films
before and after annealing at several temperatures. In view of the figures,
we can see that 4a and 4b, and 4c have different molecular self-assembly
behaviors. The 4a and 4c are easier to form continuous and dense thin
films with apparent crystalline zones, whereas 4b is apt to form highly
crystalline nanoribbon morphology with large grain boundaries. It is well
known that high crystallinity is generally beneficial for charge carrier
transport, so 4b should be expected to have the highest electron mobility
among the three small molecules. However, the 4b thin film owns larger
grain boundaries than those of 4a and 4c counterparts. Because con-
tinuous morphology could avoid the trapping of charge carrier, the large
grain boundaries in the 4b thin film are unbeneficial for charge carrier
transport. In combination with the fact that the 4c thin film owns large
crystal domains than that of 4a, the three small molecules showed
slightly increasing charge transport characteristics in their respective
thin film devices [26]. It is worth to note that the superior crystallinity of
4b might endow the material with great potential in fabricating high-
performance n-type single crystal OFET devices. Meanwhile, the high
crystallinity of the annealed 4b thin film was also confirmed by two
dimensional grazing incidence X-ray diffraction (2D-GIXRD) pattern. As
shown in Fig. 5d-f, the annealed 4a and 4c films showed similar multiple
diffraction peaks both in the out-of-plane (qz) and in-plane (qxy) direc-
tions, indicating lamellar packing modes with random orientations to the
OTS-treated substrate existing in the two films. However, the annealed
4b film exhibited a hexagonal-like diffraction pattern with a clear (010)
peak in qxy directions (Fig. 5e) [11b]. Combining the stronger and nar-
rower diffraction peaks in the 4b thin film than those in 4a and 4c
counterparts, it can be concluded that the annealed 4b thin film owns a
highly crystalline, ordered lamellar molecular packing mode with pre-
dominantly edge-on orientation to the OFET substrate.
4. Conclusion
We developed three novel nitrogen-embedded small molecules, 4a,
4b, and 4c, which were synthesized from the condensation reactions of
benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione with 1-(2-ethylhexyl)-1H-
pyrrolo[2,3-b]pyridine-2,3-dione, and its chlorine-substituted analo-
gues. The introduction and number change of chlorine atoms induced
different frontier orbital energy levels, optical properties and molecular
self-assembly behaviors of these molecule materials. Note that the 4a
and 4c thin film possess continuous morphologies with lamellar mo-
lecular packing and random orientations to the OTS-treated SiO2 sub-
strate, while the 4b thin film forms a highly crystalline morphology
with edge-on and lamellar packing as well as large grain boundaries
exist in its thin film. In consequence, the OFET devices based on 4a, 4b,
and 4c exhibited typical n-type charge transport characteristics with
slightly increasing electron mobilities. Our research reveals that the
introduction and number change of chlorine atoms is a useful approach
in regulating the optoelectronic of organic semiconducting materials.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grants 51773016, 51473021, 21673258,
621
Dyes and Pigments 163 (2019) 615–622
21774134, and 21474116), the National Key Research and
Development Program of China (2016YFB0401100 and
2017YFA0204703), and the Strategic Priority Research Program of the
Chinese Academy of Sciences (CAS) (XDB12030100). The GIXRD ana-
lyses were performed at the BL14B1 Station of Shanghai Synchrotron
Radiation Facility (SSRF). The authors are very grateful to the assis-
tance of scientists from the station during the experiments.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.dyepig.2018.12.051.
References
[1] (a) Venkateshvaran D, Nikolka M, Sadhanala A, Lemaur V, Zelazny M, Kepa M,
et al. Approaching disorder-free transport in high-mobility conjugated polymers.
Nature 2014;515:384–8;
(b) Sirringhaus H. 25th Anniversary article: organic field-effect transistors: the path
beyond amorphous silicon. Adv Mater 2014;26:1319–35;
(c) Lei YL, Deng P, Lin M, Zheng XL, Zhu FR, Ong BS. Enhancing crystalline
structural orders of polymer semiconductors for efficient charge transport via
polymer-matrix-mediated molecular self-assembly. Adv Mater 2016;28:6687–94.
[2] (a) Wang LW, Shi SW, Ma D, Chen S, Gao C, Wang M, et al. Improved photovoltaic
properties of donor–acceptor copolymers by introducing quinoxalino[2,3-b′]por-
phyrin as a light-harvesting unit. Macromolecules 2015;48:287–96.
[3] (a) Kang I, Yun HJ, Chung DS, Kwon SK, Kim YH. Record high hole mobility in
polymer semiconductors via side-chain engineering. J Am Chem Soc
2013;135:14896–9;
(b) Xue G, Zhao X, Qu G, Xu T, Gumyusenge A, Zhang Z, et al. Symmetry breaking
in side chains leading to mixed orientations and improved charge transport in
isoindigo-alt-bithiophene based polymer thin films. ACS Appl Mater Interfaces
2017;9:25426–33.
[4] (a) Lin ZZ, Liu XT, Zhang WF, Huang JY, Wang Q, Shi KL, et al.
Cyanostyrylthiophene-based ambipolar conjugated polymers: synthesis, properties,
and analyses of backbone fluorination effect. Macromolecules 2018;51:966–76.
[5] (a) Gelinck GH, Huitema HEA, Van Veenendaal E, Cantatore E, Schrijnemakers L,
Van der Putten J, et al. Flexible active-matrix displays and shift registers based on
solution-processed organic transistors. Nat Mater 2004;3:106–10;
(b) Abbel R, Galagan Y, Groen P. Roll-to-roll fabrication of solution processed
electronics. Adv Eng Mater 2018;20:1701190.
[6] (a) Wang ZG, Li ZJ, Liu J, Mei J, Li K, Li Y, Peng Q. Solution-processable small
molecules for high-performance organic solar cells with rigidly fluorinated 2,2ꞌ-
bithiophene central cores. ACS Appl Mater Interfaces 2016;8:11639–48;
(b) Yue W, Nikolka M, Xiao M, Sadhanala A, Nielsen CB, White AJP, et al.
Azaisoindigo conjugated polymers for high performance n-type and ambipolar thin
film transistor applications. J Mater Chem C 2016;4:9704–10.
[7] (a) Crone B, Dodabalapur A, Lin YY, Filas RW, Bao ZN, LaDuca A, et al. Large-scale
complementary integrated circuits based on organic transistors. Nature
2000;403:521–3;
(b) Wang CL, Dong HL, Hu WP, Liu YQ, Zhu DB. Semiconducting π-conjugated
systems in field-effect transistors: a material odyssey of organic electronics. Chem
Rev 2012;112:2208–67;
(c) Wu WB, Tang RL, Li QQ, Li Z. Functional hyperbranched polymers with ad-
vanced optical, electrical and magnetic properties. Chem Soc Rev
2015;44:3997–4022.
[8] (a) Li J, Zhao Y, Tan HS, Guo YL, Di CA, Yu G, et al. A stable solution-processed
polymer semiconductor with record high-mobility for printed transistors. Sci Rep
2012;2:754;
(b) Zhao Z, Wang ZL, Ge CW, Zhang X, Yang XD, Gao XK. Incorporation of ben-
zothiadiazole into the backbone of 1,2,5,6-naphthalenediimide based copolymers,
enabling much improved film crystallinity and charge Carrier mobility. Polym
Chem 2016;7:573–9;
(c) Wang LP, Xie XD, Shi SW, Shi KL, Mao ZP, Zhang WF, et al. Synthesis, char-
acterization, and field-effect properties of (E)-2-(2-(thiophen-2-yl) vinyl) thiophen-
based donor–acceptor copolymers. Polymer 2015;68:302–7.
[9] (a) Zhan XW, Tan ZA, Domercq B, An ZS, Zhang X, Barlow S, et al. A high-mobility
electron-transport polymer with broad absorption and its use in field-effect tran-
sistors and all-polymer solar cells. J Am Chem Soc 2007;129:7246–7;
(b) Zhou PC, Zhang ZG, Li YF, Chen XG, Qin JG. Thiophene-fused benzothiadia-
zole: a strong electron-acceptor unit to build D–A copolymer for highly efficient
polymer solar cells. Chem Mater 2014;26:3495–501;
(c) Wang B, Tsang SW, Zhang WF, Tao Y, Wong MS. Naphthodithiophene-2,1,3-
benzothiadiazole copolymers for bulk heterojunction solar cells. Chem Commun
2011;47:9471–3.
[10] (a) Luo C, Kyaw AKK, Perez LA, Patel S, Wang M, Grimm B, et al. General strategy
for self-assembly of highly oriented nanocrystalline semiconducting polymers with
high mobility. Nano Lett 2014;14:2764–71;
(b) Zhang WF, Chen ZH, Mao ZP, Gao D, Wei CY, Lin ZZ, et al. High-performance
FDTE-based polymer semiconductors with F∙∙∙H intramolecular noncovalent inter-
actions: synthesis, characterization, and their field-effect properties. Dyes Pigments
Y. Zhou et al.
2018;149:149–57.
[11] (a) Park JH, Jung EH, Jung JW, Jo WH. A fluorinated phenylene unit as a building
block for high-performance n-type semiconducting polymer. Adv Mater
2013;25:2583–8;
(b) Kang B, Kim R, Lee SB, Kwon SK, Kim YH, Cho K. Side-chain-induced rigid
backbone organization of polymer semiconductors through semifluoroalkyl side
chains. J Am Chem Soc 2016;138:3679–86.
[12] Usta H, Risko C, Wang Z, Huang H, Deliomeroglu MK, Zhukhovitskiy A, et al.
Design, synthesis, and characterization of ladder-type molecules and polymers. air-
stable, solution-processable n-channel and ambipolar semiconductors for thin-film
transistors via experiment and theory. J Am Chem Soc 2009;131:5586–608.
[13] (a) Eckstein BJ, Melkonyan FS, Manley EF, Fabiano S, Mouat AR, Chen LX, et al.
Naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide building block for semi-
conducting polymers. J Am Chem Soc 2017;139:14356–9;
(b) Chen ZH, Zhang WF, Huang JY, Gao D, Wei CY, Lin ZZ, et al. Fluorinated
dithienylethene-naphthalenediimide copolymers for high-mobility n-channel field-
effect transistors. Macromolecules 2017;50. 6098–107.
[14] Li Y, Singh SP, Sonar P. A high mobility p-type DPP-thieno[3,2-b]thiophene copo-
lymer for organic thin-film transistors. Adv Mater 2010;22:4862–6.
[15] Li S, Yuan Z, Yuan J, Deng P, Zhang Q, Sun B. An expanded isoindigo unit as a new
building block for a conjugated polymer leading to high-performance solar cells. J
Mater Chem 2014;2:5427–33.
[16] Xin HS, Ge CW, Jiao XC, Yang XD, Rundel K, McNeill CR, Gao XK. Incorporation of
2,6-connected azulene units into the backbone of conjugated polymers: towards
high-performance organic optoelectronic materials. Angew Chem Int Ed
2018;57:1322–6.
[17] Shi YQ, Guo H, Qin MC, Zhao JY, Wang YX, Wang H, et al. Thiazole imide-based all-
acceptor homopolymer: achieving high-performance unipolar electron transport in
organic thin-film transistors. Adv Mater 2018;30:1705745.
[18] Dai YZ, Ai N, Lu Y, Zheng YQ, Dou JH, Shi K, et al. Embedded electron-deficient
nitrogen atoms in polymer backbone towards high performance n-type polymer
field-effect transistors. Chem Sci 2016;7:5753–7.
[19] Shi KL, Zhang WF, Gao D, Zhang SY, Lin ZZ, Zou Y, et al. Well-balanced ambipolar
conjugated polymers featuring mild glass transition temperatures toward high-
performance flexible field-effect transistors. Adv Mater 2018;30:1705286.
[20] (a) Yao JJ, Yu CM, Liu ZT, Luo HW, Yang Y, Zhang GX, et al. Significant im-
provement of semiconducting performance of the diketopyrrolopyrrole–qua-
terthiophene conjugated polymer through side-chain engineering via hydrogen-
bonding. J Am Chem Soc 2016;138:173–85;
(b) Mei JG, Kim DH, Ayzner AL, Toney MF, Bao ZN. Siloxane-terminated solubi-
lizing side chains: bringing conjugated polymer backbones closer and boosting hole
mobilities in thin-film transistors. J Am Chem Soc 2011;133:20130–3.
[21] (a) Bronstein H, Frost JM, Hadipour A, Kim Y, Nielsen CB, Ashraf RS, et al. Effect of
622
Dyes and Pigments 163 (2019) 615–622
fluorination on the properties of a donor–acceptor copolymer for use in photo-
voltaic cells and transistors. Chem Mater 2013;25:277–85;
(b) Yum S, An TK, Wang XW, Lee W, Uddin MA, Kim YJ, et al. Benzotriazole-
containing planar conjugated polymers with noncovalent conformational locks for
thermally stable and efficient polymer field-effect transistors. Chem Mater
2014;26:2147–54.
[22] (a) Yun HJ, Kang SJ, Xu Y, Kim SO, Kim YH, Noh YY, et al. Dramatic inversion of
charge polarity in diketopyrrolopyrrole-based organic field-effect transistors via a
simple nitrile group substitution. Adv Mater 2014;26:7300–7;
(b) Hergue N, Mallet C, Savitha G, Allain M, Frere P, Roncali J. Facile synthesis of
3-alkoxy-4-cyanothiophenes as new building blocks for donor−acceptor con-
jugated systems. Org Lett 2011;13:1762–5;
(c) Lin ZZ, Liu XT, Zhang WF, Wei CY, Huang JY, Chen ZH, et al. Regioirregular
ambipolar naphthalenediimide-based alternating polymers: synthesis, character-
ization, and application in field-effect transistors. J Polym Sci Part A Polym Chem
2017;55:3627–35.
[23] (a) Kang SH, Tabi GD, Lee J, Kim G, Noh YY, Yang C. Chlorinated 2,1,3-ben-
zothiadiazole-based polymers for organic field-effect transistors. Macromolecules
2017;50:4649–57;
(b) Wei CY, Zou JB, Zhu R, Huang JY, Gao D, Wang LP, et al. Synthesis, char-
acterization, and field-effect performance of the halogenated indolone derivatives.
Dyes Pigments 2017;136:434–40.
[24] (a) Moon H, Zeis R, Borkent EJ, Besnard C, Lovinger AJ, Siegrist T, et al. Synthesis,
crystal structure, and transistor performance of tetracene derivatives. J Am Chem
Soc 2004;126:15322–3;
(b) Li J, Wang M, Ren S, Gao X, Hong W, Li H, Zhu D. High performance organic
thin film transistor based on pentacene derivative: 6,13-dichloropentacene. J Mater
Chem 2012;22:10496–500;
(c) Wang M, Li J, Zhao G, Wu Q, Huang Y, Hu W, et al. High-performance organic
field-effect transistors based on single and large-area aligned crystalline micro-
ribbons of 6,13-dichloropentacene. Adv Mater 2013;25:2229–33;
(d) Chi XL, Li DW, Zhang HQ, Chen YS, Garcia V, Garcia C, Siegrist T5. 6,11,12-
Tetrachlorotetracene, a tetracene derivative with π-stacking structure: the
Synthesis, crystal structure and transistor properties. Org Electron 2018;9:234–40.
[25] (a) Wang M, Ford MJ, Zhou C, Seifrid M, Nguyen TQ, Bazan GC. Linear conjugated
polymer backbones improve alignment in nanogroove-assisted organic field-effect
transistors. J Am Chem Soc 2017;139:17624–31;
(b) Niedzialek D, Lemaur V, Dudenko D, Shu J, Hansen MR, Andreasen JW, et al.
Probing the relation between charge transport and supramolecular organization
down to ångström resolution in a benzothiadiazole−cyclopentadithiophene copo-
lymer. Adv Mater 2013;25:1939–47.
[26] Diao Y, Shaw L, Bao ZN, Mannsfeld SCB. Morphology control strategies for solution
processed organic semiconductor thin films. Energy Environ Sci 2014;7:2145–59.