Pyrene fused perylene diimides: Synthesis, characterization and applications in organic field-effect transistors and optical limiting with high performance

Article abstract of DOI:10.1039/c5cc00966a

Three pyrene fused PDI derivatives have been obtained, in which totally different properties were observed when adopting different fusing types. For bilaterally benzannulated PDIs, through spin-coating, bottom-contact OFET devices exhibited a p-type mobility up to 1.13 cm² V^-1 s^-1, with an on/off ratio of 10⁸ in air. This journal is

Full text of DOI:10.1039/c5cc00966a

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DOI: 10.1039/C5CC00966A
COMMUNICATION
Pyrene fused perylene diimides: synthesis,
characterization and applications in organic filed-effect
transistors and optical limiting with high performance
Cite this: DOI: 10.1039/x0xx00000x
a
b
a
a
c
a
Received 00th January 2012,
Accepted 00th January 2012
Xuejun Zhan, Ji Zhang, Sheng Tang, Yuxuan Lin, Min Zhao, Jie Yang, Haoli
c b b a
Zhang,* Qian Peng, Gui Yu,* and Zhen Li*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Three pyrene fused PDI derivatives have been obtained, in reactivity of larger hydrocarbon aromatic rings and the challenge to
control structure specificity, especially for bilaterally extension.
To enrich the fused PDI family, and explore their structure-
which totally different properties were observed when
adopting different fusing type. For bilaterally benzannulation
property relationship, in this communication, three core expanded
PDI, through spin-coating, bottom-contact OFET devices
11
PDI derivatives were synthesized, in which, pyrene, an attractive
2
-1 -1
exhibited p-type mobility up to 1.13 cm V s , with an on/off
unit with unique electronic and photophysical property, was utilized
to fuse with the PDI core in different mode. To the best of our
knowledge, this is the first time that pyrene fused PDI derivatives
8
ratio of 10 in air.
Perylene tetracarboxdiimide derivatives (PDIs) have gained were designed and applied in organic electronics.
considerable attention due to their special π-conjugation structure
The synthetic route is depicted in Scheme 1, and the experimental
1
and opto-electronic properties, in addition to their exclusive details are provided in the ESI.† By utilizing the iridium-catalyzed
2
12
chemical, thermal and photochemical stability. Many PDI- reactions,
2-Bpin-7-tert-butylpyrene and 4-Bpin-2,7-di-tert-
containing conjugated molecules and polymers exhibited exciting butylpyrene were synthesized and then used to construct compounds
3
performance. For example, when utilized in organic transistors, as 1, 2 and 3 conveniently through the palladium (0)-catalyzed Suzuki
4
reported by Ichikawa et al., the tridecyl-substituted PDI showed n- cross coupling reaction, which were further cyclized to yield 4, 5 and
2
-1 -1
type mobility up to 2.1 cm V s , while an electron mobility of 6, respectively, in the presence of ferric chloride. Notably, the K-
2
-1 -1
1
.24 cm
V
s
was realized for 2,2,3,3,4,4,4-heptafluorobutyl- region of pyrene aided to eliminate the possible isomers, when
5
substituted PDI by Würthner et al. (Chart S1). Meanwhile, when cyclization reaction occurred during the synthesis of bilaterally
acting as electron acceptor in polymer solar cells instead of normal extension PDI derivative 6, since PDI-2Br is a mixture of 1,6- and
fullerenes, Nuckolls et al. achieved a high power convert efficiency 1,7-substituted ones. Interestingly, there are some differences for the
6
of 6.1% by using a helical PDI dimer (Chart S2).
dehydrocyclization reaction conditions. Compound 4 could be easily
C H
10 21
C H
10 21
C
10 21
H
Generally, there were two main approaches to design PDIs, an
easy one is the functionalization at the main or bay positions of PDI,
and another is the extension of the aromatic core of PDI, to yield
fused PDIs. Although the latter one was much more difficult with
synthetic challenge, their promising applications in different fields
prompted scientists, with great efforts, to design various heterocycle-
C
12
H
25
C
12
H
25
O
C
12
H
25
O
O
N
O
N
N
O
N
O
O
N
O
C10H21
O
O
C
O
N
O
C
7
10
H
21
fused PDIs, with the adjusted electrical characteristics, including
10
H
21
1
C
12
H
25
2
3
C
12
H
25
C
12
H
25
anthraquinone, pyridine, imidazole, pyrazole, triazole and even
naphthalene tetracarboxdiimide (NDI) or PDI itself. Interestingly, on
the other hand, as important synthetic precursors for polycyclic
aromatic hydrocarbons (PAHs), a special model to understand the
structure-property relationship of the unique graphene because of
1,6+1,7
FeCl
DCM 0 o
3
FeCl
DCM 20
3
FeCl
o
DCM 20 C
3
o
C
C
10 21
C H
C
10
H
21
10 21
C H
C
12
H
25
O
C
12
H
25
O
C
12
H
25
O
8
N
O
N
O
N
O
9
the structure similarity, fused PDIs were also required to be prepared
with different but elaborately designed structures. Thanks to the
great enthusiasm of scientists, some aromatic hydrocarbons fused
PDIs were successfully obtained, with the anthracene fused PDI as
the largest aromatic hydrocarbons fused PDI derivative up to date
O
N
O
C10H21
O
N
O
C
O
N
O
1
0
10
H
21
C
10
H
21
C
12
H
25
C
12
H
25
C
12
H
25
4
5
6
(
Chart S3). However, the family of aromatic hydrocarbons fused
Scheme 1 Synthetic route of the pyrene fused PDI derivatives.
PDIs was far from sufficient, mainly caused by the relatively bad
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0
0
0
0
0
.8
.6
.4
.2
.0
analysis of compound 4 suggests that the band at 600 nm is caused
by a transition from a pyrene-like HOMO to a PDI-like LUMO (f =
1
0
0
0
.2
.8
.4
.0
1
4
a
0
.13), while the transition in compound 1 is week (f = 0
V
.
ie
0
w
05Ar
2
ti
)
c
.
le Online
DOI: 10.1039/C5CC00966A
The cyclization precursors 1, 2 and 3, show weak emission in
DCM solutions, and their fluorescent quantum yields are estimated
to be 2.89%, 0.13% and 0.24%, respectively. After cyclization, 4
500
600
700
800
Wavelength / nm
emits at 676 nm weakly (Φ
F
= 1.21%), while compounds 5 (Φ
= 20.2%) show increased emission intensities at
30 and 635 nm, respectively. Comparing 4 and 5 carefully, the
F
=
2
6
1.1%) and 6 (Φ
F
1
4
different fused type induced a big difference of the emission
wavelengths. In addition, through transient spectra (Fig. S3) for 1, 2,
3, 4, 5 and 6, their fluorescence lifetimes were estimated to be 0.95,
3
00
400
500
600
700
800
0.48, 1.37, 5.05, 8.51 and 5.15 ns, respectively. All the fused
Wavelength / nm
0.8
0.6
0.4
0.2
0.0
compounds show increased lifetimes in comparison with their
precursors.
1
.2
.8
2
3
5
6
b
0
Cyclic voltammetry (CV) measurements were carried out to
investigate the electrochemical properties of these new PDI-based
compounds. In their CV curves, all the compounds bear two one-
electron reduction processes (Fig. S4). After cyclization, the first
oxidation potential and the first reduction potential are both
negatively shifted, indicating that they are easier to be oxidized but
more difficult to be reduced. For 1, 2, 3, 4, 5 and 6, their HOMO
values are calculated to be -5.68, 5.64, -5.59, -5.54, -5.61 and -5.45
eV, respectively. Their corresponding LUMO energy levels are
calculated to be -3.59, -3.57, -3.68, -3.68, -3.61 and -3.56 eV,
respectively. The smaller band-gap of 4 (1.86 eV) than that of 5
0.4
0.0
500
600
700
800
Wavelength / nm
2
3
5
6
3
00
400
500
600
700
800
Wavelength / nm
(
2.00 eV) further proved that the fused type in 4 can induce better
conjugation. However, with the bilateral structure, the band-gap of 6
2, 3, 5, 6 (b) in dichloromethane. The inset could be as low as 1.89 eV, owing to its enlarged planar π system.
Fig. 1 UV-vis absorption and fluorescence emission (inset)
spectra of (a) and
1
,
4
pictures are photographs under sunlight.
To obtain some information at the molecular level, we have
carried out Density Functional Theory (DFT) calculations
(
B3LYP/6-31G*) of these compounds to obtain the optimized
gotten, when its precursor, compound 1, reacted with 10 equivalent
o
structures and orbital distributions of HOMO and LUMO energy
levels. As demonstrated in Fig. 2, the electron clouds of HOMO
energy levels are all mainly located on the pyrene units, while the
LUMOs are dominated by orbitals from perylene bisimides. While
for 6, because of the extended conjugation, the electron clouds of
HOMO energy level are more delocalized. Theoretical calculated
HOMO and LUMO energy levels and band-gaps are shown in Table
S1. The predicted values of band-gaps for cyclization products 4, 5,
of ferric chloride at 0 C for 30 min. But for 5, adopting another
o
fusing type, higher temperature (20 C) and longer reaction time (70
min) were required, probably due to the different reactivity of the 1-
and 5-positions of pyrene unit or/and the different distances between
1
3
the dehydrogenation sites (Fig. S2). All of these compounds were
easily purified by column chromatography on silica gel using
1
petroleum ether-chloroform as eluent, and fully characterized by H
1
3
and C NMR, mass spectrometry, and elemental analysis, with the
data presented in the ESI.
6
are calculated to be 2.22, 2.41, 2.32 eV, respectively, about 0.4 eV
larger than their optical band-gaps.
The research of organic field-effect transistors (OFETs) is of great
importance to the development of radio frequency identification
Thanks to the long branched alkyl chains, all the compounds have
good solubility in common organic solvents, such as
dichloromethane, chloroform and tetrahydrofuran (THF) et al.. Fig. 1
shows their absorption spectra in diluted dichloromethane (DCM)
solutions. Compound 1 and 2, with a donor-acceptor (D-A) structure,
show similar absorptions, in which the bands around 350 and 500
nm can be respectively attributed to the absorption of pyrene and
perylene bisimide unit. Dipyrene substituted PDI (3) shows similar,
however, broader absorption in the long wavelength region (400-650
nm) possibly derived from its D-A-D structure, similar to the UV-vis
absorption of dianthrancene substitution PDIs reported in
(
RFID) tags, flexible displays, electronic papers, sensors, and so
1
4
forth. Even though lots of π-conjugated systems have been
developed for OFETs, those with high mobility over 1.0 cm V
and easily to be solution-processed are still scarce. Considering its
large planar structure, special electronic property, and good
solubility, the mobility of 6 was tested. OFETs were fabricated in a
2
-1 -1
s
3
c
“
bottom-contact” configuration. Before the deposition of organic
semiconductors, source and drain electrodes made of gold were pre-
prepared on the SiO /Si substrates. The octyltrichlorosilane (OTS)
1
0b
2
literature. After cyclization, absorptions of the pyrene units are
red-shifted (about 50 nm), while the absorptions of perylene
bisimide units are blue-shifted, as the results of the enlarged
1
1
conjugation. For 4 and 5, due to the different fusing types, the
1
0
typical shoulder bands caused by HOMO-LUMO transition appear
at around 600 or 570 nm, respectively, which partially reflects the
better electron delocalization of the fused type in 4. For bilaterally
extension 6, the absorbance of perylene bisimide is relatively low,
and two new peaks around 560 and 613 nm are observed.
Theoretical calculation was also carried out by the TD-DFT method
at the B3LYP/6-311G (d, p) level to investigate the electronic Fig. 2 Calculated molecular orbital amplitude plots of HOMO
transitions (Fig. S3-S5, Table S1-S2). The electronic transition
(
down) and LUMO (up) levels of 1, 2, 3a, 4, 5 and 6.
2
| J. Name., 2012, 00, 1‐3
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To know more about the influence of thermal treatments on the
devices performance, thin film morphologies of 6 spin-coated on the
OTS modified SiO
2
/Si were studied by X-ray diffracti
V
o
i
n
ew
(
A
X
rt
R
icl
D
e O
)
n
a
line
n
d
DOI: 10.1039/C5CC00966A
atomic force microscopy (AFM). Fig. 4 and S5 show the AFM
topography images of pristine thin films of 6 and thermally treated
ones at different temperatures. As shown in Fig. 4b, no obvious
crystallinity was found in the as-prepared film. On the contrary, a
degree of crystallinity was found in thin film under Tannealing=80 °C
(
T
Fig. S5b). The AFM images then change dramatically when
annealing increases above 120 °C, and thermal cracks begin to appear
over 200 °C, which is an adverse factor for charge transport (Fig.
S5c-f). According to XRD patterns (Fig. 4), two groups of peaks, i.e.
Fig. 3 Transfer (a) and output (b) characteristics of an OFET
device based on
4
.85° and 9.63°, 2.96° and 5.85° are found under 120 °C and 200 °C,
16
6
2
, spin coated on OTS-treated SiO /Si substrate which corresponds to d-spacing of 1.82 nm and 2.98 nm,
and annealed at 160 °C.
respectively. Under 160 °C, a combination of two groups appears,
suggesting the formation of polymorphism. On the contrast, no
peaks appeared under RT and 80 °C. From the viewpoint of
relationship between molecular packing and mobility (Table S2), we
could draw a conclusion that the d-spacing of 2.98 nm is more
favourable to carrier transport, thus the carrier mobility increases
with the Tannealing. It is also worth noting that the carrier mobility
decreases below 200 °C due to the numerous thermal cracks, as
mentioned above.
a
o
2
5 C
o
8
0 C
o
1
20 C
o
1
60 C
o
2
00 C
o
2
40 C
1.0
0.9
0.8
0.7
Tannealing
o
a
[
C ]
5
10
Degree [
15
o
]
4
5
6
Fig. 4 Temperature variable XRD pattern (a) and AFM images
o
of the thin films of
6 (b: pristine film, c: annealed at 160 C).
treatment was performed on the gate dielectrics, which were placed
in a vacuum oven with OTS at a temperature of 120 C to form an
OTS self-assembled monolayer. Then the thin film were spin-coated
o
0.6
50 -40 -30 -20 -10
Z (mm)
-
0
10 20 30 40 50
2
on the OTS modified SiO /Si substrates from the chloroform
-1
1.0
0.9
.8
solutions (10 mg mL ) and followed by thermal annealing. The
OTFTs characteristics of the devices were all determined at room
temperature in air. Representative transfer and output characteristics
of the transistors are presented in Fig. 3.
b
0
o
0.7
0.6
Excitedly, when thermally annealed at 160 C, thin-film devices
6
exhibited excellent p-type transistor behaviours with high mobility
2
-1 -1
8
Io=3.3 J
up to 1.13 cm V
s and an on/off ratio of 10 . To confirm the
0
.5
.4
.3
Io=32 J
results, another batch of seven devices were fabricated, and the
Io=108 J
2
-1 -1
0
average mobility are calculated to be 0.877 cm V s with a
standard deviation (sample) of 0.172. To our best knowledge, the
hole mobility is the highest one among pyrene derivatives (Chart S4),
close to the hole mobility of highly purified pyrene judged from
0
-
50 -40 -30 -20 -10
0
10 20 30 40 50
Z (mm)
3
c
transient photocurrent and overlap integrals. Further raised the Fig. 5 Open-aperture Z-scan results of
4
,
5
and
6
with the same
with different
o
annealing temperature to 200 C resulted in lower mobility of 0.64 input fluencies of 10.8 μJ (a) and results of
6
2
-1 -1
2
-1 -1
cm V s , which was still above 0.5 cm V s . It was also noticed
input fluencies (b).
that at the V value of -70 V, the output curve decreased rapidly at
G
the VDS values in the range of -30 to -50 V, then increased to the
original currency, much apparent in comparison with other output
curves at other VG values. This indicated that the OFET devices
might be not so stable, and further improvements should be
considered to enhance the stability.
Noticed that delocalized π-conjugation systems have been used for
optical limiting application, however, no such experimental reports
17
concerned on PDI derivatives. To fully investigate the opto-
electronic properties of 6, we also measured their optical limiting
performance. And actually, materials with excellent nonlinear
optical (NLO) responses continue to be the focus of theoretical and
experimental research due to their potential applications in optical
communication, optical data storage, photodynamic therapy and
Interestingly, after optimization, the highest electron mobility was
-5
2
-1 -1
only about 10 cm V
s even in inert atmosphere, indicating that
the main carriers in 6 are holes. The observed excellent p-type
transport behaviour of 6, which is so far unprecedented for PDIs,
should be related to its structural features that influence the
molecular packing, possibly leading to the formed “pyrene-channel”
18
photonic devices. Thus, an open-aperture Z-scan technique was
used to measure the NLO absorption coefficient. The results of
cyclized products are presented in Fig. 5. The input laser intensity
was 10.8 μJ and linear transmittances of all samples were adjusted to
1
5
in the thin films.
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7
3%. 5 and 6 show an obvious reduction in the transmission on
4
5
S. Tatemichi, M. Ichikawa, T. Koyama and Y. Taniguchi, Appl. Phys.
focusing the lens, the minimal normalized transmittance of 6 can
reach 63%. As shown in Fig. 5b, better nonlinear optical response
emerged when increasing the input intensity. At a lower intensity of
Lett., 2006, 89, 112108.
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DOI: 10.1039/C5CC00966A
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3
.3 μJ, the transmittance was 74%, then dropped to be 50% when the
Würthner, J. Am. Chem. Soc., 2009, 131, 6215.
intensity increased to 32 μJ, and further decreased to 37% at the
intensity of 108 μJ. From the curve shape of open-aperture Z-scan 6 Y. Zhong, M. T. Trinh, R. Chen, W. wang, P. P. Khlyabich, B. Kumar,
results at 108 μJ, the stability of compound 6 is deduced. And it can
be expected that the transmittance will be further decreased when
increasing the input intensity. These results show that compound 6 is
a good candidate for optical limiting applications.
Q. Xu, C. Y. Nam, M. Y. Sfeir, C. Black, M. L. Steigerwald, Y. L. Loo,
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1
7
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In summary, three pyrene fused PDIs derivatives (4, 5 and 6) were
successfully obtained, after conquering the challenge for the control
of the structure specificity. The different fused mode of 4 and 5
induces totally different properties, while 6 is a bilaterally extension
PDI derivative. Easy fabricated OFET devices based on spin-coated
,
Paek, J. Song, C. Kim, N. Cho and J. Ko, Chem. Commun., 2011, 47
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,
2
-1 -1
film of 6 exhibit the hole mobility as high as 1.13 cm V
s and an
5
8
on/off ratio of 10 in air. Thanks to its special electronic structure, as
utilized in optical limiting, 6 also showed excellent performance, and
the transmittance can decrease to 37%, when the input laser intensity
was 108 μJ. These results, coupled with the good stability, make 6
potential applications in the organic electronic field. Thus, the
synthetic method presented in this paper might open up a new way to
eliminate the PDI isomers in the cyclization reactions and for the
preparation of larger hydrocarbon aromatic rings, perhaps, graphene
nanoribbons.
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Acknowledgements
We are grateful to the National Science Foundation of China
(
no. 21325416), and the National Fundamental Key Research
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2
Notes and references
a
Department of Chemistry, Hubei Key Lab on Organic and Polymeric
1
1
Opto-Electronic Materials, Wuhan University, Wuhan, 430072, China.
E-mail: lizhen@whu.edu.cn or lichemlab@163.com; Fax: +86-27-
(
,
2
6
b
8756757; Tel: +86-27-68755363.
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