Semi-perfluoroalkylated perylene diimides for conjugated polymers with high molecular weight and high electron mobility

Article abstract of DOI:10.1002/pola.28880

Perylene diimides (PDIs) and their derivatives are excellent semiconductors, while conjugated polymers based on PDIs have limited applications because of their low electron mobility (μ_e) derived from low molecular weight. The reported maximum number-average molecular weight (M_n) of related polymers is only 21 kDa because PDIs have very poor solubility due to strong π–π stacking of their big planar conjugated cores. Herein, it is found that suitable semi-perfluoroalkyl groups could enhance the solubility of PDIs significantly, and a series of semi-perfluoroalkyl modified conjugated polymers with high molecular weight and electron mobility were synthesized. The maximum M_n reaches 94.8 kDa [P(4C_F8C_H-PDI-T2)_HW]. In their space-charge-limited current (SCLC) devices, all polymers exhibit typical characters of electron transporting semiconductors, and the highest μ_e is up to 8.40 × 10^?3 cm²?V^?1?s^?1 [P(4C_F8C_H-PDI-T2)_HW], which is similar as that of widely used electron transporting semiconductor PC₆₁BM (6.41 × 10^?3?cm²?V^?1?s^?1).

Full text of DOI:10.1002/pola.28880

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Semi-Perfluoroalkylated Perylene Diimides for Conjugated Polymers with
High Molecular Weight and High Electron Mobility
1
1
1,2
1,2
1
Chunsheng Cai, Ji Wan, Youdi Zhang, Zhongyi Yuan
,
1,2
Qingfang Huang,
1
,2
1
1
Guodong Xu, Yu Hu, Xiaohong Zhao, Yiwang Chen
1
College of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031, China
2
Jiangxi Provincial Key Laboratory of New Energy Chemistry/Institute of Polymers, Nanchang University, 999 Xuefu Avenue,
Nanchang 330031, China
Correspondence to: Z. Yuan (E-mail: yuan@ncu.edu.cn)
Received 14 August 2017; accepted 26 September 2017; published online 00 Month 2017
DOI: 10.1002/pola.28880
ABSTRACT: Perylene diimides (PDIs) and their derivatives are
excellent semiconductors, while conjugated polymers based
on PDIs have limited applications because of their low electron
n F H
maximum M reaches 94.8 kDa [P(4C 8C -PDI-T2)HW]. In their
space-charge-limited current (SCLC) devices, all polymers
exhibit typical characters of electron transporting semiconduc-
2
3
2
21 21
mobility (l
e
) derived from low molecular weight. The reported
) of related
tors, and the highest l
[P(4C 8C -PDI-T2)HW], which is similar as that of widely used
electron transporting semiconductor PC61BM (6.41
e
is up to 8.40 3 10
cm
V
s
maximum number-average molecular weight (M
n
F
H
polymers is only 21 kDa because PDIs have very poor solubility
due to strong p–p stacking of their big planar conjugated cores.
Herein, it is found that suitable semi-perfluoroalkyl groups
could enhance the solubility of PDIs significantly, and a series
of semi-perfluoroalkyl modified conjugated polymers with high
molecular weight and electron mobility were synthesized. The
3
23
2
21 21
1
0
cm
V
s
). V
C
2017 Wiley Periodicals, Inc. J. Polym. Sci.,
Part A: Polym. Chem. 2017, 00, 000–000
KEYWORDS: electron mobility; molecular weight; perylene dii-
mides; semi-perfluoroalkyl
INTRODUCTION Organic semiconductors are important elec-
Conjugated polymers based on PDIs have low MW due to
tronic materials which offer attractive prospect for flexible
strong p–p stacking of big rigid cores of PDIs. For example, rep-
resentative copolymers poly{[N,N -bis-(1-hexylheptyl)-perylene-
1
–3
0
and low-cost electronic photoelectric.
Polymeric semicon-
0
ductors have the advantages of solution processing, good
3,4,9,10-tetracarboxylic
diimide-1,7-diyl]-alt-(2,2 -bithiophene-
4
–6
0
0
film-forming ability, and high carrier mobility.
Excellent
5,5 -yl)} [P(13C
H
-PDI-T2)] and poly{[N,N -bis-(10-nonadecyl)-
perylene-3,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-(2,2 :5 ,2 -
0
0
00
electron acceptors (n-type semiconductors, electron trans-
porting materials) are much rarer compared with their coun-
terpart electron donors (p-type semiconductors, hole
0
terthiophene-5,5 -yl)} [P(19C
-PDI-T3)] (structures are in Sup-
H
porting Information, Fig. S1) show number-average molecular
7
–9
25,26
transporting materials).
Hence, it is urgent to develop
n
weight (M ) of 15.1 and 6.8 KDa, respectively.
To obtain sol-
highly efficient polymeric electron acceptors.
uble conjugated polymers based on PDIs, bulky branched alkyl
side chains have to been adopted, while large insulated alkyl
groups are unfavorable for charge transport. Therefore, it is
challengeable to obtain conjugated polymer based on PDIs with
high MW and high electron mobility.
Perylene diimides (PDIs) and their derivatives with strong
absorption and large rigid conjugated cores are proved to be
1
0–15
excellent acceptors.
They have shown various applica-
tions in organic solar cells, field-effect transistors, and photo-
1
6–22
conductors.
However, conjugated polymers based on
Perfluoroalkyl groups with the compact and rigid structure
have high thermal and chemical stability, regular arrange-
ments, and well resistance to water. They play important
PDIs show limited applications because of their low electron
mobility derived from their low molecular weight (MW).
Mobility of conjugated polymers can be much improved by
reaching sufficiently high MW, which is attributed to stronger
in-plane-oriented p–p stacking and longer conjugated chains
2
7–29
roles in the field of semiconductor and self-assembly.
0
Organic field-effect transistors (OFETs) based on N,N -
bis-(2,2,3,3,4,4,4-heptafluorobutyl)-PDI (3C 1C -PDI, Fig. 1)
F H
2
3,24
2
21 21
without defects.
show electron mobility as high as 1 cm
V
s
, and
Additional Supporting Information may be found in the online version of this article.
2017 Wiley Periodicals, Inc.
V
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2
3
2
21 21
le is up to 8.40 3 10 cm ꢁV ꢁs [P(4C 8C -PDI-T2) ],
F
H
HW
23
which is similar as that of PC BM (6.41
3 10
6
1
2
21 21 10
cm ꢁV ꢁs ).
EXPERIMENTAL
Materials and Methods
Unless stated otherwise, solvents and chemicals were
obtained commercially and were used without further
purification.
1
13
19
H NMR, C NMR, and F NMR spectra were measured on
an NMR spectrometer with CDCl as the solvent. Absorption
3
spectra were recorded on a PerkinElmer lambda 750 Spec-
trophotometer. Cyclic voltammetry (CV) was performed with
an electrochemical analyzer with a three-electrode system.
Working electrode: glassy carbon; reference electrode: Ag/
AgCl; auxiliary electrode: Pt wire; electrolyte: tetrabutylam-
monium hexafluoro-phosphate (Bu NPF ); internal standard:
F H F H
FIGURE 1 Structures of 3C 1C -PDI, 4C 8C -PDI, and polymer
F H
P(4C 8C -PDI-T2). [Color figure can be viewed at wileyonline-
library.com]
4
6
ferrocene (Fc). Thermogravimetric analysis (TGA) measure-
ments were performed using a TGA Mettler-Toledo Gmbh
perfluoroalkyl groups could form compact and ordered
3
0–32
stacking which favors for efficient charge-transfer.
ever, N,N -di(perfluoroalkyl)-PDIs show very poor solubility,
How-
21
0
under flowing air at a heating rate of 10 Kꢁmin . The
molecular weights and dispersity were measured by high-
temperature gel permeation chromatography (GPC) on Cirrus
at 160 8C using 1,2,4-tri-chlorobenzene as an eluent and
polystyrene as the standard.
which makes their low-cost solution process impossible.
Semi-perfluoroalkyl groups with both fluorinated and hydro-
genated carbons have special characters for electronic materi-
3
3,34
als.
Semi-perfluoroalkylated conjugated compounds have
Charge Carrier Mobility
much better solubility than their perfluoroalkylated counter-
3
5,36
The charge carrier mobility was measured by the SCLC
method with the electron-only device of ITO/ZnO/Active
layer/Al for the electron mobility measurement. After meas-
urements of the J–V curves of the devices, the electron
mobility was calculated according to the following equation:
parts.
The strong self-organization of semi-perfluoroalkyl
segments resulted in a high degree of long-range order in
polymer crystallites. These unique organizational features
gave rise to high electron mobility of semi-perfluoroalkylated
3
7
naphthalene diimides (NDIs) polymers, far higher than those
of polymers with regular alkyl chains.
V2
L3
9
J5 ErE0l
8
Hence, we are interested in semi-perfluoroalkylated PDIs and
they are expected to be solution processable and retain the
advantages of perfluoroalkyl groups. It is found that semi-
perfluoroalkyl groups have significant effect on the solubility of
PDIs, and highly soluble PDIs can be obtained with suitable
where E is the dielectric constant of the polymer, E is the
r
0
permittivity of the vacuum, l is the zero-field mobility, J is
0
the current density, L is the thickness of the blend films,
V 5 Vappl 2 V , V
is the applied potential, and Vbi is the
bi
appl
0
side chains. For example, the N,N -bis-(1,1,1,2,2,3,3,4,4-nona-
built-in potential from the difference in the work function of
fluorododecan-6-yl)-perylene diimide (4C 8C -PDI in Fig. 1)
F
H
the anode and the cathode (in the electron-only device, V
value is 0 V).
bi
shows the solubility higher than 680 mg/mL in CH Cl . Thus, it
39,40
2
2
is possible to construct soluble conjugated polymers with semi-
perfluoroalkylated PDIs based on their ultrahigh solubility.
Accordingly, a series of semi-perfluoroalkylated PDI copolymers
P(C C -PDI-T) with different donor parts and semi-
Synthesis of 1,1,1,2,2,3,3,4,4-nonafluoro-6-iododecane (4C 6C -
F
H
I): A mixture of nonafluoro-1-iodobutane (4C -I) (73.8 mmol,
F
F
H
25.5 g), 1-hexene (147.5 mmol, 12.4 g), Na SO (118.0 mmol,
2
3
perfluoroalkyl chains were designed and obtained. Bithiophene
and terthiophene were chosen as donor units because they are
excellent donor parts in organic semiconductors.
14.9 g), and DMF (250 mL) were stirred at 60 8C for 6 h. The
reaction mixture was extracted with CH Cl , dried with MgSO ,
2
2
4
and purified through silica gel column to give a colorless liquid
41,42
4
C 6C -I (22.4 g, 71%).
F H
In this research, all the polymers are with M > 66.3 kDa,
n
0
and the highest M
n
reaches 94.8 kDa for poly{[N,N -bis-
Synthesis of 6-azido-1,1,1,2,2,3,3,4,4-nonafluorodecane (4C 6C -
F H
(
1,1,1,2,2,3,3,4,4-nona-fluorododecan-6-yl)-perylene-3,4,9,10-
N ): A mixture of 4C 6C -I (52.1 mmol, 22.4g), NaN (0.2 mol,
3 F H 3
0
0
tetracarboxylic diimide-1,7-diyl]-alt-(2,2 -bithiophene-5,5 -yl)}
P(4C 8C -PDI-T2) , Fig. 1], which is much more higher
10.2 g), and DMSO (160 mL) was added. The reaction was
stirred at 100 8C for 6 h. The product was extracted with
CH Cl , washed with salt water, dried with MgSO , and concen-
[
F
H
HW
2
5,26,38
than reported ones (M
charge-limited current (SCLC) devices, all polymers with
high electron mobility (>10 cm V
n
ꢀ 15.1 kDa).
In their space-
2
2
4
trated. A yellow oily liquid was obtained, crude 4C 6C -N
3
F
H
24
2
21 21
43
s
), and the highest
(18.0 g).
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Synthesis of 7,7,8,8,9,9,10,10,10-nonafluorodecan-5-amine
(d, 8H), 5.73 (s, 2H), 3.35 (m, 2H), 2.55 (m, 2H), 2.37 (m,
1
3
(
4C 6C -amine): A mixture of 4C 6C -N (40.5 mmol,
2H), 1.94 (m, 2H), 1.31 (d, 8H), 0.87 ppm (s, 6H); C NMR
(100 MHz, CDCl ) d: 163.7, 134.8, 132.3, 131.4, 129.6, 126.5,
123.5, 123.2, 122.8, 110.0, 53.4, 46.4, 32.5, 28.5, 22.3, 13.9
F
H
F
H
3
14.0 g), 5% Pd/C (1.0 g), and methanol (100 mL) was
3
stirred at room temperature for 10 h at hydrogen atmo-
sphere. The crude product was purified through silica gel
column, and colorless and transparent liquid 4C 6C -amine
1
9
ppm; F NMR (376.5 MHz, CDCl
2115.53, 2124.91, 2126.37 ppm; HRMS (MALDI-TOF):
) d: 281.47, 2114.71,
3
F
H
1
2
(
11.3 g, 87%) was obtained. H NMR (600 MHz, CDCl
3
) d:
Calcd for C44
H
F
32
N
18
2
O
4
, 994.2075, found: 994.2163 (M ).
3
.26 (s, 1H), 2.08 (m, 2H), 1.34 (d, 8H), 0.88 ppm (s, 3H);
0
1
3
The procedure for the synthesis of N,N -bis-(1,1,1,2,2,3,3,4,4-
C NMR (150 MHz, CDCl ) d: 45.1, 41.2–34.7, 27.8, 22.5,
3
1
9
nonafluorododecan-6-yl)-perylene-3,4,9,10-tetracarboxylic dii-
mide (4C 8C -PDI), N,N -bis-(7,7,8,8,9,9,10,10,11,11,12,12,12-
tridecafluorododecan-5-yl)-perylene-3,4,9,10-tetracarboxylic dii-
mide (6C 6C -PDI), and N,N -bis-(9,9,10,10,11,11,12,12,13,13,
4,14,14-tridecafluorotetradecan-7-yl)-perylene-3,4,9,10-tet-
racarboxylic diimide (6C 8C -PDI) is similar as that of
4C 6C -PDI.
13.8 ppm; F NMR (565 MHz, CDCl ) d: 281.34, 2112.33,
3
0
F
H
2
112.82, 2113.66, 2114.21, 2124.81, 2126.16 ppm; HRMS
(
ESI, m/z): [M 1 H] calcd for C H F N, 320.1061, found:
1
0 15 9
0
F
H
320.1059.
1
The procedure for the synthesis of 1,1,1,2,2,3,3,4,4-nona-
fluorododecan-6-amine (4C 8C -amine), 7,7,8,8,9,9,10,10,11,
F
H
F
H
F
H
1
1,12,12,12-tridecafluorododecan-5-amine (6C 6C -amine),
F H
F H F H
Synthesis of 4C 8C -PDI: PDA (20.6 mmol, 8.1 g), 4C 8C -
amine (61.9 mmol, 21.5 g), and imidazole (150.0 g) were
and 9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluorotetra-
decan-7-amine (6C 8C -amine) is the same as that of
F
H
used and stirred at 145 8C for 4.5 h under argon. 4C 8C -
F
H
4C 6C -amine.
F H
PDI was obtained (19.2 g, 88%) as the dark red solid. mp:
258 8C; UV–vis (CHCl ): max (E) 5 527 nm (74,200
cm ); H NMR (400 MHz, CDCl ) d: 8.68 (d, 8H), 5.72
(s, 2H), 3.34 (m, 2H), 2.54 (m, 2H), 2.35 (m, 2H), 1.93 (s,
1
For 4C
F
8C
H
-amine: Transparent liquid (14.3 g, 82%);
H
3
k
21
21
1
NMR (400 MHz, CDCl ) d: 3.31 (s, 1H), 2.26–2.00 (m, 2H),
M
3
3
1
3
1.30 (d, 12H), 0.88 ppm (s, 3H); C NMR (100 MHz, CDCl3)
1
3
d: 118.3, 116.2, 45.0, 38.4, 38.3, 38.0, 31.7, 29.1, 25.7, 22.5,
2H), 1.28 (d, 16H), 0.82 ppm (s, 6H); C NMR (100 MHz,
CDCl ) d: 163.6, 134.8, 132.3, 131.4, 129.6, 126.5, 123.5,
123.2, 123.1, 122.8, 53.4, 46.4, 32.9, 32.4, 31.6, 28.9, 26.3,
1
9
14.0 ppm; F NMR (376.5 MHz, CDCl ) d: 281.41, 2112.33,
3
3
2
112.85, 2113.73, 2114.22, 2124.86, 2126.17 ppm; HRMS
1
9
(
ESI, m/z): [M 1 H] calcd for C H F N, 348.1374, found:
22.5, 14.0 ppm; F NMR (376.5 MHz, CDCl
114.73, 2115.56, 2124.88, 2126.37 ppm; HRMS (MALDI-
TOF): Calcd for C H F N O , 1050.2701, found:
3
) d: 281.48,
1
2 19 9
2
348.1370.
4
8 40 18 2 4
1
2
For 6C 6C -amine: Transparent liquid (13.2 g, 85%);
H
F
H
1050.2791 (M ).
NMR (600 MHz, CDCl ) d: 3.30 (s, 1H), 2.13 (m, 2H), 1.40
3
1
3
Synthesis of 6C 6C -PDI: PDA (16.1 mmol, 6.3 g), 6C 6C -
(
4
m, 8H), 0.92 ppm (s, 3H); C NMR (150 MHz, CDCl
5.2, 38.6, 38.5, 38.3, 38.0, 27.9, 22.5, 13.8 ppm; F NMR
3
) d:
F
H
F
H
1
9
amine (48.2 mmol, 20.2 g), and imidazole (120.0 g) were
used and stirred at 145 8C for 4 h under argon. 6C 6C -PDI
(
565 MHz, CDCl ) d: 281.05, 2112.10, 2112.58, 2113.43,
F
H
3
was obtained (16.3 g, 85%) as the dark red solid. mp:
2113.91, 2121.95, 2123.03, 2123.85, 2126.33 ppm; HRMS
2
M
04 8C; UV–vis (CHCl3): kmax (E) 5 527 nm (82,300
(
4
ESI, m/z): [M 1 H] calcd for C H F N, 420.0997, found:
20.0994.
1
2 15 13
21
21
1
cm ); H NMR (400 MHz, CDCl ) d: 8.69 (d, 8H), 5.72
3
(
s, 2H), 3.34 (m, 2H), 2.54 (m, 2H), 2.36 (m, 2H), 1.93 (m,
1
13
For 6C 8C -amine: Transparent liquid (10.9 g, 89%);
H
2H), 1.36 (d, 8H), 0.86 ppm (s, 6H); C NMR (100 MHz,
F
H
NMR (400 MHz, CDCl ) d: 4.93 (s, 2H), 3.38 (s, 1H), 2.20-
CDCl ) d: 163.6, 134.8, 134.7, 132.3, 131.4, 129.5, 126.5,
3
3
1
3
2.21 (d, 2H), 1.29 (m, 10H), 0.87 ppm (s, 3H); C NMR (100
124.80–124.3, 123.2, 122.8, 53.4, 46.4, 32.7, 28.5, 22.3, 13.9
1
9
MHz, CDCl ) d: 46.2, 45.14, 38.6, 38.4, 38.3, 31.7, 29.0, 25.6,
ppm; F NMR (376.5 MHz, CDCl ) d: 281.24, 2114.47,
3
3
1
9
2
2.5, 13.8, 11.4 ppm;
F NMR (376.5 MHz, CDCl
3
) d:
2115.32, 2122.26, 2123.31, 2123.97, 2126.62 ppm; HRMS
2
2
80.93, 2111.29, 2114.51, 2121.90, 2122.99, 2123.73,
126.26 ppm; HRMS (ESI, m/z): [M 1 H] calcd for
(MALDI-TOF): Calcd for C H F N O , 1194.1947, found:
1194.1893 (M ).
4
8 32 26 2 4
2
C H F N, 448.1310, found: 448.1308.
1
4 19 13
Synthesis of 6C 8C -PDI: PDA (15.9 mmol, 6.0 g), 6C 8C -
amine (45.9 mmol, 20.5 g), and imidazole (120.0 g) were
F
H
F
H
0
Synthesis of N,N -bis-(7,7,8,8,9,9,10,10,10-nonafluorodecan-5-
yl)-perylene-3,4,9,10-tetracarboxylic diimide (4C 6C -PDI):
F
H
used and stirred at 145 8C for 6 h under argon. 6C 8C -PDI
F
H
A mixture of Perylene-3,4,9,10-tetracarboxylic dianhydride
was obtained (16.5 g, 86%) as the dark red solid. mp:
(
1
2
PDA) (20.6 mmol, 8.1 g), 4C 6C -amine (62.0 mmol,
9.8 g), and imidazole (150.0 g) was stirred at 145 8C for
h under argon. The reaction mixture was extracted with
207 8C; UV–vis (CHCl3): kmax (E) 5 527 nm (76,700
F
H
21
21
1
M
cm ); H NMR (400 MHz, CDCl ) d: 8.68 (d, J 5 29.6
3
Hz, 8H), 5.71 (s, 2H), 3.34 (m, 2H), 2.54 (m, 2H), 2.35 (m,
1
3
CH
2
Cl
2
, washed with dilute HCl, and purified through silica
1H), 1.93 (m, 2H), 1.45–1.11 (d, 16H), 0.82 ppm (s, 6H);
C
gel column with eluent of the mixture of petroleum ether
and CH Cl . 4C 6C -PDI (15.5 g, 76%) was obtained as the
NMR (101 MHz, CDCl ) d: 163.7, 134.8, 132.3, 131.4, 129.6,
3
2
2
F
H
126.5, 126.3, 123.5, 123.3, 123.2, 122.9, 53.4, 46.4, 33.0,
1
9
red solid. mp: 272 8C; UV–vis (CHCl ): k
(E) 5 527 nm
32.6, 31.6, 28.9, 26.4, 22.5, 14.0 ppm; F NMR (376.5 MHz,
3
max
21
21
1
(
85,500 M cm ); H NMR (400 MHz, CDCl ) d: 8.70
CDCl ) d: 281.24, 2114.47, 2115.37, 2122.26, 2123.32,
3
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2
123.97, 2126.61 ppm; HRMS (MALDI-TOF): Calcd for
polymerization mixture was poured into 100 mL of methanol.
Subsequently, the polymer precipitated as a purple black solid,
was dried in a vacuum drying oven, and purified through silica
2
C H F N O , 1250.2573, found: 1250.2469 (M ).
5
2 40 26 2 4
0
Synthesis of 1.7-dibromo-N,N -bis-(7,7,8,8,9,9,10,10,10-nona-
fluorodecan-5-yl)- perylene-3,4,9,10-tetracarboxylic diimide
3 F H
gel column with eluent of CHCl . P(4C 6C -PDI-T2) was
obtained (328.6 mg, 71%) as the black solid. M 5 74.9 KDa,
n
(Br-4C 6C -PDI): A mixture of 4C 6C -PDI (5.8 mmol,
F H F H
M /M 5 1.77; UV–vis (CHCl ): k
max
(E)5 362 nm (30,200
3
) d 8.76 (d, 2H), 8.43–
w
21
n
3
5.8 g), K CO (157.1 mmol, 21.7 g), FeBr (1.0 mmol, 0.3 g),
21
1
2
3
3
M
cm ); H NMR (500 MHz, CDCl
and CH Cl (100 mL) was stirred at 45 8C. Br2 solution
2
2
8
.37 (d, 4H), 7.33–7.18 (d, 4H), 5.71 (s, 2H), 3.34 (s, 2H), 2.52
(20 mL Br in 20 mL CH Cl ) was added to the mixture. The
19
2
2
2
(s, 2H), 2.36 (s, 2H), 1.91 (s, 2H), 1.31 (d, 8H), 0.87 (s, 6H);
F
reaction lasted for 24 h. Then the reaction mixture was
added to an ice–Na SO (20.0 g)–H O mixture with stirring.
The product was extracted with CH Cl , washed with water,
NMR (376.5 MHz, CDCl ) d 34.23, 281.51, 2114.70, 2115.48,
3
2
3
2
2124.91, 2126.38.
2
2
dried with MgSO , and concentrated. Compound Br-4C 6C -
0
4
F
H
The procedure for the synthesis of poly{[N,N -bis-(1,1,1,2,2,
,3,4,4-nonafluorododecan-6-yl)-perylene-3,4,9,10-tetracarbox-
PDI (5.1 g, 76%) was obtained as a red solid after purifica-
3
1
tion through a silica gel column. mp: 115 8C; H NMR (400
0
0
ylic diimide-1,7-diyl]-alt-(2,2 -bithiophene-5,5 -yl) P(4C
PDI-T2) , P(4C 8C -PDI-T2) P(4C 8C -PDI-T2)
HW,
y{[N,N -bis-(1,1,1,2,2,3,3,4,4-nonafluorododecan-6-yl)-perylene-
,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-(2,2 :5 ,2 -terthio-
phene-5,5 -yl)} P(4C 8C -PDI-T3), and poly{[N,N -bis-(9,9,10,
0,11,11,12,12,13,13,14,14,14-tridecafluorotetradecan-7-yl)-per-
ylene-3,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-(2,2 -bithio-
0
phene-5,5 -yl)} P(6C 8C -PDI-T2) is similar as that of
F H
F H
8C -
MHz, CDCl ) d 9.51 (d, 2H), 8.95 (d, 2H), 8.72 (m, 2H), 5.71
3
pol-
LW
F
H
MW,
F
H
(
s, 2H), 3.36 (d, 2H), 2.52 (s, 2H), 2.35 (s, 2H), 1.92 (s, 2H),
0
1
3
1
1
1
.31 (d, 8H), 0.87 (s, 6H); C NMR (100 MHz, CDCl
3
) d
0 0 00
0
3
62.7, 138.9, 138.0, 133.2, 133.0, 129.3, 127.2, 123.3, 122.9,
0
F
H
1
9
22.6, 122.2, 46.6, 32.6, 28.4, 22.3, 13.9; F NMR (376.5
281.45, 2114.84, 2115.55, 2124.90,
126.37. MS (MALDI-TOF): Calcd for C H Br F N O ,
1
MHz, CDCl
2
1
3
)
d
0
4
4
30
2
18
2
4
2
152.03, found: 1152.55 (M ).
P(4C 6C -PDI-T2).
F
H
0
The procedure for the synthesis of 1.7-dibromo-N,N -bis-
1,1,1,2,2,3,3,4,4-nonafluorododecan-6-yl)- perylene-3,4,9,10-
tetracarboxylic diimide (Br-4C 8C -PDI) and 1.7-dibromo-
Synthesis of P(4C 8C -PDI-T2) : Br-4C 8C -PDI (0.3 mmol,
F
H
LW
F
H
(
0
0
362.6 mg), 2,2 -bis(trimethylstannyl)-5,5 -bithiophene (0.3
F
H
mmol, 147.6 mg), Pd (dba) (0.006 mmol, 5.5 mg), P(o-Tol)
2
3
3
0
N,N -bis-(9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluorote-
tradecan-7-yl)- perylene-3,4,9,10-tetracarboxylic diimide (Br-
(
0.05 mmol, 14.6 mg), and dry toluene (10 mL) were used.
The reaction mixture was refluxed for 10 h under argon.
P(4C 8C -PDI-T2) was obtained (318.3 mg, 87%) as the
6
C 8C -PDI) is the same as that of Br-4C 6C -PDI.
F H F H
F
H
LW
black solid. M 5 48.7 kDa, M /M 5 1.74.
1
n
w
n
For Br-4C 8C -PDI: Red solid (5.4 g, 80%); mp: 112 8C; H
F
H
NMR (400 MHz, CDCl ) d: 9.50 (d, 2H), 8.94 (d, 2H), 8.71
3
Synthesis of P(4C 8C -PDI-T2)MW: Br-4C 8C -PDI (0.3
F H F H
(
1
m, 2H), 5.69 (s, 2H), 3.34 (d, 2H), 2.51 (s, 2H), 2.34 (s, 2H),
.90 (s, 2H), 1.23 (s, 16H), 0.83 (s, 6H); C NMR (100 MHz,
0
0
mmol, 362.5 mg), 2,2 -bis(trimethylstannyl)-5,5 -bithiophene
0.3 mmol, 147.6 mg), Pd (dba) (0.006 mmol, 5.5 mg), P(o-
1
3
(
2
3
CDCl ) d: 168.2–157.0, 139.1–138.7, 138.4–137.7, 133.3,
3
Tol)3 (0.05 mmol, 14.6 mg), and dry toluene (10 mL) were
used. The reaction mixture was refluxed for 48 h under
1
33.1, 130.8, 130.1, 129.4, 128.8, 127.3, 123.4, 123.1, 46.8,
1
9
33.0, 31.7, 29.0, 26.4, 22.6, 14.1; F NMR (376.5 MHz,
argon. P(4C 8C -PDI-T2) was obtained (282.0 mg, 78%)
MW
F
H
CDCl ) d: 281.46, 2114.81, 2115.57, 2124.91, 2126.40;
3
as the black solid. M 5 79.2 KDa, M /M 5 1.76. UV–vis
n w n
MS (MALDI-TOF): Calcd for C H Br F N O , 1208.09,
21
21
1
4
8
38
2
18
2
4
(CHCl ): k
(E)5 364 nm (31,500 M cm ); H NMR (400
3
max
2
found: 1208.51 (M ).
MHz, CDCl ) d 8.76 (d, 2H), 8.43 (s, 4H), 7.33–7.11 (m, 4H),
3
5
.71 (s, 2H), 3.36 (s, 2H), 2.52 (s, 2H), 2.35 (s, 2H), 1.91 (s,
1
For Br-6C 8C -PDI: Red solid (4.7 g, 78%); mp: 95 8C;
H
19
F
H
2H), 1.26 (s, 16H), 0.83 (s, 6H); F NMR (376.5 MHz, CDCl ) d
3
NMR (400 MHz, CDCl
3
) d 9.50 (s, 2H), 8.94 (d, 2H), 8.72 (d,
H), 5.70 (s, 2H), 3.34 (s, 2H), 2.50 (s, 2H), 2.33 (s, 2H),
.90 (s, 2H), 1.24 (s, 16H), 0.84 (s, 6H); C NMR (100 MHz,
) d 162.9, 138.8, 138.0, 133.1, 133.0, 130.8, 130.0,
29.3, 127.2, 123.3, 122.9, 122.6, 122.2, 120.9, 46.6, 33.0,
2
34.23, 281.50, 2114.70, 2115.46, 2124.85, 2126.37.
2
1
1
3
Synthesis of P(4C
mmol, 362.5 mg), 2,2 -bis(trimethylstannyl)-5,5 -bithiophene
(0.3 mmol, 147.6 mg), Pd (dba) (0.006 mmol, 5.5 mg), P(o-
Tol)3 (0.05 mmol, 14.6 mg), and dry toluene (10 mL) were
used. The reaction mixture was refluxed for 72 h under
F
8C
H
-PDI-T2)HW
:
Br-4C
F
8C
H
-PDI (0.3
0
0
CDCl
3
1
3
2
3
1
9
1.6, 28.8, 26.2, 22.6, 13.9; F NMR (376.5 MHz, CDCl ) d
81.23, 2114.54, 2115.30, 2122.25, 2123.30, 2124.00,
3
2
2
126.57; MS (MALDI-TOF): Calcd for C H Br F N O ,
argon. P(4C 8C -PDI-T2)
as the black solid. M 5 94.8 kDa, M /M 5 1.55.
n w n
was obtained (289.0 mg, 80%)
HW
5
2
38
2
26
2
4
F
H
2
1408.08, found: 1408.35 (M ).
0
Synthesis of poly{[N,N -bis-(7,7,8,8,9,9,10,10,10-nonafluorode-
Synthesis of P(4C 8C -PDI-T3): Br-4C 8C -PDI (0.3 mmol,
362.6 mg), 1,1 -(2,2 :5 ,2 -terthiophene)-5,5 -diybis(1,1,1-tri-
methylstannane) (0.3 mmol, 172.2 mg), Pd (dba) (0.006
2 3
F
H
0
F
H
00
0
0
00
can-5-yl)-perylene-3,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-
2,2 -bithiophene-5,5 -yl)} P(4C
C 6C -PDI (0.4 mmol, 399.3 mg), 2,2 -bis(trimethylstannyl)-
,5 -bithiophene (0.4 mmol, 196.7 mg), Pd (dba) (0.008 mmol,
0
0
(
F
6C
H
-PDI-T2): A mixture of Br-
0
4
5
7
mmol, 5.5 mg), P(o-Tol) (0.05 mmol, 14.6 mg), and dry tolu-
F
H
3
0
ene (10 mL) were used. The reaction mixture was refluxed
for 96 h under argon. P(4C 8C -PDI-T3) was obtained
2
3
.3 mg), P(o-Tol)3 (0.05 mmol, 14.6 mg), and dry toluene
F
H
(10 mL) was stirred at 110 8C for 12 h under argon. The
(272.6 mg, 70%) as the black solid. M 5 73.7 kDa, M /
n w
4
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F H
SCHEME 1 Synthetic route for conjugated polymers P(C C -PDI-T). [Color figure can be viewed at wileyonlinelibrary.com]
M
M
n
5 2.46; UV–vis (CHCl
cm ); H NMR (600 MHz, CDCl ) d 8.81 (s, 1H), 8.74
3
):
k
max (E) 5 400 nm (40,400
synthesized according to Scheme 1. New amines (4C
amine and 4C 8C -amine) and known ones (6C 6C -amine
and 6C 8C -amine) were obtained by a new synthetic route,
F H
6C -
2
1
21
1
3
F
H
F
H
(
s, 1H), 8.39 (d, 4H), 7.32 (s, 2H), 7.21 (s, 2H), 5.76 (s, 2H),
F
H
3
1
.37 (s, 2H), 2.59 (s, 2H), 2.39 (s, 2H), 1.94 (s, 2H), 1.29 (s,
which is through the transformation of semi-perfluoroalkyl
iodide into amines by the substitution and hydrogenation,
and every reaction yield is higher than 70%.
1
9
6H), 0.86 (s, 6H); F NMR (565 MHz, CDCl ) d 2113.78
3
4
1–45
(
s), 2114.19 (s), 2115.07 (s), 2115.52 (s), 2124.37 (s),
125.89 (s).
2
4
C 6C -PDI, 6C 6C -PDI, 4C 8C -PDI, and 6C 8C -PDI were
F
H
F
H
F
H
F
H
obtained as red solids by the condensation of PDA with the
corresponding C C -amine in imidazole. These C C -PDIs
Synthesis of P(6C 8C -PDI-T2): Br-6C 8C -PDI (0.3 mmol,
F
H
F
H
0
0
422.6 mg), 2,2 -bis(trimethylstannyl)-5,5 -bithiophene (0.3
F
H
F H
were isolated and purified through silica gel column in excel-
lent yields of 75%–88%.
mmol, 147.6 mg), Pd (dba) (0.006 mmol, 5.5 mg), P(o-Tol)
2
3
3
(
0.05 mmol, 14.6 mg) and dry toluene (10 mL) were used.
The reaction mixture was refluxed for 12 h under argon.
P(6C 8C -PDI-T2) was obtained (288.0 mg, 67%) as the
Bromination of 4C 6C -PDI, 4C 8C -PDI, and 6C 8C -PDI at
F
H
F
H
F
H
F
H
4
5 8C in CH Cl leads to Br-4C 6C -PDI, Br-4C 8C -PDI, and
2 2 F H F H
black solid. M 5 66.3 KDa, M /M 5 2.29; UV–vis (CHCl ):
n
w
n
3
Br-6C 8C -PDI in 76%, 80%, and 78% yield, respectively.
2
1
21
1
F
H
kmax (E) 5 364 nm (28,100 M cm ); H NMR (500 MHz,
Longer reaction time and higher Br
multibrominaton of C -PDIs.
2
concentration lead to
CDCl ) d 8.76 (d, 2H), 8.43 (s, 4H), 7.24 (d, 4H), 5.71 (s, 2H),
3
F H
C
3
1
2
.34 (s, 2H), 2.52 (s, 2H), 2.34 (s, 2H), 1.92 (s, 2H), 1.26 (s,
1
9
6H), 0.83 (s, 6H); F NMR (376.5 MHz, CDCl
81.31, 2122.26, 2123.31, 2123.89, 2126.65.
3
) d 234.17,
The polymers P(4C 6C -PDI-T2), P(4C 8C -PDI-T2) ,
F H F H LW
P(4C 8C -PDI-T2)
,
P(4C 8C -PDI-T2)
P(4C 8C -PDI-
F H
F
H
MW
F
H
HW,
T3), and P(6C 8C -PDI-T2) were synthesized by Pd-catalyzed
F
H
Stille-coupling reactions in yields of 67%–87%. By control-
ling the reaction time, polymers P(4C 8C -PDI-T2) with dif-
RESULTS AND DISCUSSION
F
H
Synthesis
ferent MW were obtained. P(4C 8C -PDI-T2) , P(4C 8C -
F
H
LW
F
H
Semi-perfluoroalkylated PDIs (C C -PDIs) with different side
PDI-T2)MW, and P(4C 8C -PDI-T2)
are with Mn of 48.7,
F
H
F
H
HW
chains and corresponding polymers P(C C -PDI-T) were
79.2, and 94.8 kDa, respectively. Mn of the other polymers
F
H
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TABLE 1 Solubility of C
F
C
H
-PDIs in different solvents (mg/mL,
CH Cl ). As 6C 6C -PDI shows poor solubility, we prepared
2 2 F H
at room temperature)
polymers with the other three semi-perfluoroalkyl groups.
Compound
Toluene
CH
2
Cl
2
THF
All semi-perfluoroalkylated polymers have good solubility in
common solvents such as chloroform, chlorobenzene, and o-
dichlorobenzene (o-DCB), and their solubility is higher than
4C
F
4C
F
6C
F
6C
F
6C
H
8C
H
6C
H
8C
H
-PDI
-PDI
-PDI
-PDI
98
423
5
44
3
686
18
80
3
2
5 mg/mL in CHCl , which guarantees solution process of
3
these polymers.
23
17
6
Optical Properties
w n
are higher than 66.3 KDa (M /M < 2.5). The MW of these
To better understand special characteristics of semi-
perfluoroalkylated polymers, we first studied basic proper-
ties of C C -PDIs. The absorption of C C -PDIs was shown in
polymers are much higher than that of PDI polymers with
0
regular alkyl side chains. Poly{[N,N -bis-(1-hexylheptyl)-pery-
F
H
F H
lene-3,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-(2-thiophen-
Supporting Information, Figure S2 and Table S1. In solution,
they all demonstrate the strong visible absorption in 400–
0
5
-yl)} [P(13C -PDI-T)] and poly{[N,N -bis-(1-hexylheptyl)-pery-
H
lene-3,4,9,10-tetracarboxylic diimide-1,7-diyl]-alt-(2,20-bithio-
phene-5,50-yl)} [P(13C -PDI-T2)] (structures are in Support-
5
50 nm, with maximum extinction coefficients (Emax) of
21 21
H
74,200–85,500 M
cm . All the solid absorptions show
ing Information, Fig. S1) show M
n
20.5 and 8.0 kDa, respec-
obvious red-shift by 58–98 nm compared to solution absorp-
2
6,46
tively.
Regular alkylated PDI polymers are usually with
tions, which is attributed to the J-type molecular aggregation
4
7
bulky branched side chains, while semi-perfluoroalkylated pol-
ymers in this research are with side chains with 10, 12, and
in solid state. All four compounds show the same emission
profile (Supporting Information, Fig. S3) and their fluores-
cence quantum yields are higher than 0.93, which makes
them promising fluorescent dyes.
14 carbons (Scheme 1). So, PDI with small size semi-
perfluoroalkyl groups could enhance the solubility obviously
and lead to conjugated polymers with high MW.
The solution absorption of semi-perfluoroalkylated polymers
P(C C -PDI-T) was shown in Figure 2. The detailed parame-
The structures of new compounds 4C 6C -amine, 4C 8C -
F
H
F
H
F
H
amine, 4C 6C -PDI, 6C 6C -PDI, 4C 8C -PDI, 6C 8C -PDI,
F
H
F
H
F
H
F
H
ters are summarized in Table 2. Polymers P(4C 6C -PDI-T2),
F H
Br-4C 6C -PDI, Br-4C 8C -PDI, and Br-6C 8C -PDI were well
F
H
F
H
F
H
P(4C 8C -PDI-T2) , and P(6C 8C -PDI-T2) exhibit similar
F H MW F H
1
13
19
characterized by H NMR, C NMR, F NMR, and MS. And
the polymers P(4C 6C -PDI-T2), P(4C 8C -PDI-T2)MW
P(4C 8C -PDI-T3), and P(6C 8C -PDI-T2) were characterized
absorption profile with three main absorption peaks, indicat-
ing the similar electronic effect of different side chains to the
conjugated cores in solution. Their maxima extinction coeffi-
F
H
F
H
,
F
H
F
H
1
19
4
21
21
by GPC, H NMR, and F NMR.
cient (Emax) is around 3.0 3 10
M
cm
located at
3
64 nm. Compared with P(4C 8C -PDI-T2)MW, obvious batho-
F
H
Solubility
chromic shift of absorption spectra of the P(4C 8C -PDI-T3)
was observed, which can be attributed to stronger electron
donating ability of terthiophene.
F
H
The solubility is an important parameter for their solution
process of organic semiconductors. Solubility of 4C 6C -PDI,
F
H
6
C 6C -PDI, 4C 8C -PDI, and 6C 8C -PDI in toluene,
F H F H F H
dichloromethane, and THF were measured at room tempera-
ture, as shown in Table 1. Compared with insoluble N,N -
All these semi-perfluoroalkylated polymers show strong solid
absorption in the range of 300–800 nm. The solid absorption
edge of P(4C 8C -PDI-T3) shows obvious red shift of 20 nm
0
di(perfluoroalkyl)-PDIs, C C -PDIs are readily soluble in
F
H
F
H
common organic solvents. Different semi-perfluoroalkyl
groups lead to different solubility for PDIs, and 4C 8C -PDI
shows the largest solubility (>400 mg/mL in toluene and
compared to the corresponding edge in solution, which is
attributed to the intermolecular aggregation in the solid film.
F
H
Calculated optical band gaps (E ) of these polymers are
g
2
5
F H 3
FIGURE 2 Absorption spectra of polymers P(C C -PDI-T) in CHCl (left, 10 M) and solid film (right). [Color figure can be viewed
at wileyonlinelibrary.com]
6
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TABLE 2 Optical and electrochemical properties of polymers P(C
F
C
H
-PDI-T)
bs
ka (nm)
a
21
21
b
c
Polymers
Solution
Film
E
max (M cm
)
k
on set (nm)
E
g
(eV)
LUMO (eV)
HOMO (eV)
P(4C
P(4C
P(4C
P(6C
6C
F H
8C
F H
8C
F H
8C
F H
-PDI-T2)
-PDI-T2)MW
-PDI-T3)
-PDI-T2)
362/480/614
364/480/606
400/504/634
364/482/612
362/478/602
362/478/600
404/512/654
360/480/596
30,200
31,500
40,400
28,100
787
778
780
765
1.58
1.59
1.59
1.62
24.17
24.06
24.14
24.21
25.75
25.65
25.73
25.83
a
c
The molar extinction coefficient at kmax in solution.
Measured in thin films.
Optical band gap.
b
between 1.58 and 1.62 eV, and the minimum value is about
372–388 8C (Supporting Information, Fig. S6), and all the
2
5
0.1 eV lower than that of regular alkylated polymers.
polymers show T higher than 364 8C (Supporting Informa-
d
tion, Fig. S7). The dense self-segregation of the fluoro alkyl
chains contributes high thermal stability of these polymers.
3
1
Electrochemical Properties
F H
Electrochemical properties of four C C -PDIs were measured
by cyclic voltammetry (CV) method. The results are shown
in Supporting Information, Figure S4 and Table S1. The cal-
culated LUMO energy levels were 23.85 to 23.86 eV with
ferrocene as the internal standard, and the value is 0.14–
Phase Properties
To obtain phase properties of four C C -PDIs, their differen-
tial scanning calorimetry (DSC) curves were measured. The
results are displayed in Supporting Information, Figure S8.
DSC results show that 6C 6C -PDI and 6C 8C -PDI are both
F
H
0.15 eV lower than that of regular alkylated PDIs, which
F
H
F
H
indicates the stronger electron accepting ability of C C -
PDIs.
with a single melting and a freezing peak in the heating and
cooling processes, respectively, and no mesophase was
F
H
4
8
F H F H
observed. While 4C 6C -PDI and 4C 8C -PDI show two and
The CV results of polymers P(C C -PDI-T) are shown in Sup-
F
H
three phase transfer peaks, respectively, which indicates that
they have one and two mesophases. POM images (Support-
ing Information, Fig. S9) show that polarized light can pass
though films of 4C 6C -PDI and 4C 8C -PDI at mesophase
porting Information, Figure S5 and Table 2. All polymers dis-
play two reversible reductive waves, which suggest the
polymers could accept at least two electrons. The LUMO
energy levels of these polymers were calculated to be 24.06
to 24.21 eV, and the value is lower than those of polymers
F
H
F
H
temperature, which suggests that 4C 8C -PDI and 4C 6C -
F
H
F
H
PDI are typical liquid crystals. As is well known, liquid crys-
tals can form the ordered packing which is favor for the
2
6
(
LUMO 5 23.8 eV) with regular alkyl chains, which is con-
sistent with low LUMO energy levels of C C -PDIs. The low-
52–54
F
H
charge transfer.
lying LUMO energy levels derive from strong electron-
withdrawing properties of semi-perfluoroalkyl groups, and it
From the DSC thermograms of all polymers P(C C -PDI-T)
F
H
2
0,49–51
makes these polymers strong electron acceptors.
(Supporting Information, Fig. S10), no obvious exotherm or
endotherm peaks were observed from 50 to 250 8C, which
means that these polymers are amorphous.
5
5
Thermal Stability
The thermal character of four small molecules C C -PDIs
F
H
and four polymers P(C C -PDI-T) were measured by ther-
Charge Transport Properties
F
H
mogravimetric analysis (TGA). C
mal stability with a high 5% weight loss temperature (T
F
C
H
-PDIs exhibit good ther-
) of
The electron-transporting properties were measured by
SCLC method on the Mott–Gurney equation, which is widely
d
F H
FIGURE 3 Plots for the measurements of electron mobility of all polymers P(C C -PDI-T) pure device by SCLC method with the
electron-only devices of ITO/ZnO/pure polymer/Al.
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TABLE 3 Molecular weights and electron mobility values of the polymers
a
a
w
a
2
21 21
s
Polymer
M
n
(kDa)
M
(kDa)
M /M
w n
l
e
(cm V
)
24
25
24
23
24
24
P(4C
P(4C
P(4C
P(4C
P(4C
P(6C
6C
F H
8C
F H
8C
F H
8C
F H
8C
F H
8C
F H
-PDI-T2)
74.9
48.7
79.2
94.8
73.7
66.3
132.8
85.0
1.77
1.74
1.76
1.55
2.46
2.29
8.20 3 10
1.04 3 10
5.02 3 10
8.40 3 10
7.20 3 10
5.81 3 10
-PDI-T2)LW
-PDI-T2)MW
-PDI-T2)HW
-PDI-T3)
13.9
147.1
181.1
152.2
-PDI-T2)
a
n w w n
Number-average molecular weight (M ), weight-average molecular weight (M ), and polydispersity index (M /M ) determined by high-
temperature GPC at 160 8C using 1,2,4-tri-chlorobenzene as the solvent and polystyrene with narrow molecular weight distribution as the standard.
applied to evaluate the charge transporting ability in organic
ACKNOWLEDGMENTS
4
0,55
optoelectronics.
The current–voltage plots for the mobil-
The work was supported by grants National Natural Science
Foundation of China (No. 21562031 and 21602150), Natural
Science Foundation of Jiangxi Province in China (No.
ity were shown in Figure 3, and the electron mobility values
are listed in Table 3.
2
0161BAB213064, 20171ACB21012, 20161BAB213063, and
The electron mobility of polymers P(4C
F H
8C -PDI-T2) with
2
5
20142BAB213005), and the Innovation Fund Designated for
Graduate Students of Nanchang University (No. cx2016049).
low, middle, and high MW are found to be 1.04 3 10 , 5.02
2
4
23
2
21 21
3
10 , and 8.40 3 10
higher electron mobility of P(4C 8C -PDI-T2)
HW
cm ꢁV ꢁs , respectively. The
could be
F
H
attributed to the high MW (M 5 94.8 kDa), because higher
CONFLICT OF INTEREST
n
MW is beneficial to the charge transfer in polymer main
chains, in which polymer itself is more likely to form molec-
ular stacking orderly and excellent films. The other three
polymers of the electron mobility are in the same order of
The authors declare no competing financial interest.
24
2
21 21
10
cm V
s
, which could be ascribed to the high MW
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