Synthesis and photoelectric properties of donor-acceptor-donor molecule containing perylene diimide

Article abstract of DOI:10.14233/ajchem.2014.17040

In this paper, a novel perylene diimide derivative 1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide (PDI-TPA) was synthesized and characterized by IR spectroscopy, 1H NMR and elemental analysis. Besides, solubility and photoelectric properties of 1,7-bis[N,N-bis(4- phenyl)aniline]perylene diimide were studied. Results show that 1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide exhibits excellent solubility in common solvents. The absorption bands span a wide range of the visible spectra and optical band gap is 1.68 eV. In addition, 1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide exhibits an ambipolar behaviour, the highest occupied molecular orbital (HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) energy level are -5.64 eV and -3.94 eV, respectively.

Full text of DOI:10.14233/ajchem.2014.17040

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Asian Journal of Chemistry; Vol. 26, No. 23 (2014), 8049-8052
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.17040
Synthesis and Photoelectric Properties of Donor-Acceptor-Donor
Molecule Containing Perylene Diimide
*
CHUN MING JIAO, BING JUN LI, SI LI YI and QING XU
Faculty of Materials Science and Chemical Engineering, State Key Laboratory Base of Novel Functional Materials and Preparation Science,
Ningbo University, Ningbo 315211, P.R. China
*Corresponding author: Tel: +86 13566358956; E-mail: xuqing@nbu.edu.cn; jld670541cmgf@163.com
Received: 16 January 2014;
Accepted: 10 April 2014;
Published online: 15 November 2014;
AJC-16291
In this paper, a novel perylene diimide derivative 1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide (PDI-TPA) was synthesized and
characterized by IR spectroscopy, 1H NMR and elemental analysis. Besides, solubility and photoelectric properties of 1,7-bis[N,N-bis(4-
phenyl)aniline]perylene diimide were studied. Results show that 1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide exhibits excellent
solubility in common solvents. The absorption bands span a wide range of the visible spectra and optical band gap is 1.68 eV. In addition,
1,7-bis[N,N-bis(4-phenyl)aniline]perylene diimide exhibits an ambipolar behaviour, the highest occupied molecular orbital (HOMO)
energy level and the lowest unoccupied molecular orbital (LUMO) energy level are -5.64 eV and -3.94 eV, respectively.
Keywords: Perylene diimide, Synthesis, Photoelectric properties.
INTRODUCTION
EXPERIMENTAL
Recently, perylene diimides (PDIs) have been application
extensively in molecular electronic devices such as photo-
voltaic cells, organic field-effect transistors (OFETs) and light-
emitting diodes (OLEDs), because of their favorable properties
for this purpose, such as migrational, photochemically,
thermally stability and so forth. These materials have excellent
fluorescent properties with high photoluminescence quantum
yields1-5. However, a key issue for perylene diimides is their
solvent solubility, which restricts their thin-film-forming
capability and potential applications as solution processable
semi-conductors6-8. Previous studies9-12 have shown that
introduction of bulky alkyl, alkoxy, aryloxy moiety into the
perylene diimides backbone can enhance solubility in many
aprotic solvents and exhibited excellent thin-film-forming
capability.
All other chemicals and reagents were purchased from
Aladdin and used as received without any further purification
unless otherwise specified.All the reactions were accomplished
in distilled anhydrous solvents under inert atmosphere. The
1H NMR spectral data of synthesized samples were recorded
on a Bruker ACF 300 spectrometer operating at 400 MHz for
1H nucleus, using CDCl3 solvent and TMS as internal standard,
respectively. The absorbance and fluorescence spectra were
recorded on a Shimadzu 3101 PC spectrophotometer and Hitachi
F-4600 spectrofuoro-meter, respectively. Cyclic voltammo-
grams measurements have been carried out using 0.1 M tetra-
butylammonium perchlorate (TBAP) as supporting electrolyte
in dichloro-methane solutions at a scan rate of 100 mV/s, The
electrochemical cell composed of three electrode system,
glassy carbon as working electrode, platinum rod as a counter
electrode and saturated calomel as reference electrode.
The synthetic route of 1,7-bis[N,N-bis(4-phenyl)aniline]-
perylene diimide (PDI-TPA) is shown in Scheme-I.
In addition, the long alkoxy chains and triphenyl amine
moiety have also been further derivatised to modify specific
optical properties such as electronic energy levels and absor-
ption wavelength13,14. In this paper, we have used perylene tetra-
carboxylic dianhydride (PCD) as raw materials via Suzuki-
coupling reaction to obtain a novel donor-acceptor-donor (D-
A-D) molecule PDI-TPA. Effects of 3-(2-ethyl-hexoxy)
propylamine and triphenyl amine moiety on solubility and
photoelectronic properties of perylene diimides were investi-
gated.
Synthesis of compound 2: A mixture of perylene tetracar-
boxylic dianhydride (PCD) (19.6 g, 0.05 mol) and 300 mL
concentrated sulfuric acid was stirred for 12 h at room tempe-
rature and subsequently I2 (0.48 g, 1.89 mmol) was added.
The reaction mixture was heated to 85 °C and bromine (5.83
mL, 0.1 mol) was added dropwise over a time period of 8 h.
After bromine addition, the reaction mixture was heated for

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8050 Jiao et al.
Asian J. Chem.
O
O
O
N
O
O
Br
O
O
O
O
O
O
O
O
O
O
O
O
Br2, H2SO4
85 °C, 4 h
3-(2-ethylhexoxy) propylamine
Br
NMP, CH3COOH
150 °C, 24 h
Br
Br
PCD
2
N
O
N
N
B(OH)2
O
N
O
O
N
O
PDI-Br
O
O
Pd(PPh 3 )4 , K2CO3
Toluene, 100 °C, 24 h
N
PDI-TPA
Scheme-I: Synthetic routes of PDI-TPA
an additional 10 h at 85 °C and cooled to room temperature.
The excess bromine was removed by a gentle stream of N2
and 50 mL of water was added carefully. The resulting preci-
pitate was separated by filtration through a funnel, washed
with 300 mL of 86 % sulfuric acid and a large amount of
water and dried in a vacuum to obtain the compound 2 (23.85
g, 85 %). IR (KBr, νmax, cm-1) 1771, 1739, 1726, 1592, 1376,
1286, 1230, 1166, 1139, 1037, 957, 859, 805, 734, 694.
Synthesis of compound PDI-Br: Compound 2 (2.20 g,
4 mmol), NMP (60 mL), n-butyric acid (40 mL) and 3-(2-ethyl
hexoxy)propylamine (2.64 mL, 12 mmol) were mixed in a
250 mL three-neck flask while maintain a good stirring, The
mixture was degassed and refluxed for 24 h at 150 °C under
N2 purge. After being cooled, the mixture was poured into
100 mL methanol and stored at -10 °C whole night. The formed
precipitate was collected by filtration and washed with
methanol. The precipitate was purified on a silica gel column
with CH2Cl2 : petroleum (v:v, 10:1) as eluent to afford the dye
PDI-Br as red solid (2.46 g, 70 %). 1H NMR (400 MHz, CDCl3,
δ ppm) 9.37(d, J = 8.0 Hz, 2H), 8.83 (s, J = 8.0 Hz, 2H),
8.61(d, J = 6.4 Hz, 2H), 4.16 (t, J = 5.2 Hz, 4H), 3.56 (t, J =
5.6 Hz , 4H), 3.26 (t, J = 5.6 Hz, 4H), 2.04 (t, J = 6.0 Hz, 4H),
1.15 (m, 18H), 0.75 (m, 12H).Anal. Calcd for C46H52N2O6Br2:
C, 62.17; H, 5.90; N, 3.15. found: C, 62.06; H, 5.98; N, 3.09.
Synthesis of compound PDI-TPA: Compound PDI-Br
(2.66 g, 3 mmol), 4-4-(diphenyl-amino)phenylboronic acid
(1.83 g, 6.33 mmol), Pd(PPh3)4 (0.1 g. 0.08 mmol), K2CO3
water solution (17.4 mL, 2 M) and dried toluene (80 mL) were
added to a 50 mL three-neck flask while maintain a good stirring.
The mixture was degassed and refluxed for 24 h at 100 °C
under N2 purge. After being cooled, the mixture was poured
into 100 mL methanol and stored at -10 °C whole night. The
formed precipitate was collected by filtration and washed with
methanol. The precipitate was purified on a silica gel column
with CH2Cl2: petroleum (v:v, 1:1) as eluent to afford compound
PDI-TPA (2.30 g, 63 %). IR (KBr,νmax, cm-1) 2958, 2927, 2858,
1696, 1658, 1587, 1493, 1274, 1182, 1109, 861, 812, 694. 1H
NMR (400 MHz, CDCl3, δ ppm) 8.63 (s, J = 8.0 Hz, 2H), 8.23
(d, J = 8.0 Hz, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.32 (m, 12H),
7.20 (m, 8H), 7.13 (m, 8H), 4.30 (t, J = 6.4 Hz, 4H), 3.54 (t,
J = 6.0 Hz, 4H), 3.26 (t, J = 5.6 Hz, 4H), 2.03 (m, 4H), 1.19-
1.33 (m, 18H), 0.77-0.84 (m, 12H). Anal. Calcd for
C82H80N4O6: C, 80.89; H, 6.62; N, 4.60; found: C 80.51; H,
7.35; N, 5.15.
RESULTS AND DISCUSSION
Synthesis: Synthesis of PDI-TPA began with the I2-
catalyzed bromination of perylene tetracarboxylic dianhydride
in 98 % conc. sulfuric acid15. PDI-Br could be conveniently
obtained in good yield by direct condensation using NMP and
acetic acid as the solvent. Suzuki coupling of PDI-Br and
4-(diphenyl-amino)phenyl boronic acid with Pd(PPh3)4 as

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Vol. 26, No. 23 (2014)
Synthesis and Photoelectric Properties of Donor-Acceptor-Donor Molecule 8051
0.8
0.6
0.4
0.2
0
catalyst and toluene as solvent at 100 °C under nitrogen atmos-
phere reflux conditions for 24 h, successfully produces PDI-
TPA with a high yield. The chemical structure of PDI-TPA was
fully characterized by IR, 1H NMR spectra, elemental analysis,
etc. The 1H NMR spectrum is depicted in Fig. 1.
PDI-Br solution
PDI-TPA solution
PDI-Br film
PDI-TPA film
PDl-Br
400
500
600
Wavelength (nm)
700
800
Fig. 2. Normalized absorption spectra of the solutions and thin films of
perylene diimides (PDIs)
PDl-TPA
7.4 7.3 7.2 7.1
because the introduction of triphenylamine units enhanced the
degree of intramolecular charge transfer. As compare to those
of in the solutions, the absorption bands of the films are shifted
to the higher wavelength region due to solid state aggregation
and increasing amorphous nature. In addtion, in the case of
PDI-TPA, the starts absorption from 740 nm region with a lower
optical bandgap of 1.68 eV compare to PDI-Br (2.19 eV),
which is due to effective π-π conjugation of electron rich
triphenylamine unit18.
10
8
6
4
2
0
ppm
Fig. 1 1H NMR spectra of perylene diimides (PDIs)
PDI-Br has only one singlet appears at 8.83 ppm in the
aromatic region, the result is consistent with the highly symme-
tric structure. The proton of PDI-TPA aromatic region appears
at 7.1-8.2 ppm due to the triphenyl amine moiety had been
introduced. The elemental analysis is also in good agreement
with the chemical structure.
Fluorescence spectra properties: Emission spectra of
the dilute solutions at fixed optical density using an excitation
wavelength of 330 nm are shown in Fig. 3.
Solubility: Solubility behavior of resulting perylene diimides
was tested qualitatively and the results are summarized in
Table-1. PDI-TPA exhibited highly soluble in common solvents
such as CHCl3, C6H5CH3, THF, CH2Cl2 etc compare with PCD,
which is due to the introduction of the bulky 3-(2-ethyl-
hexoxy)propylamine unit directly attached to the perylene core
reduces the π-stacking ability of the perylene moieties, thus
increasing its solubility16. 1,7-Bis[N,N-bis(4-phenyl)aniline]-
perylene diimide such excellent solubility in common organic
solvents are competitive as candidates for solution processable
semiconductor.
350
300
250
200
150
100
50
Br-PDl
TPA-PDl
Absorption spectra properties: Absorption spectra of
the solutions of perylene diimides with a concentration of
10-6 M and of spin coated thin flms are depicted in Fig. 2.
TPA-Br shows an absorbtion band peak at 524 nm with
characteristic vibronic fine structure which is attributed to the
perylene core π-π* transition17. The λmax = 630 nm of PDI-TPA
is red shifted about 106 nm compared with that of PDI-Br
0
–50
400
500
600
700
Wavelength (nm)
Fig. 3. Normalized emission spectra of perylene diimides (PDIs)
TABLE-1
SOLUBILITY OF PERYLENE DERIVATIVES
CHCl3
-
C6H5CH3
DMF
+ +
+
THF
+
NMP
+ +
+
CH2Cl2
-
PCD
-
PDI-Br
PDI-TPA
+ +
++
+ +
+ +
+ +
+
+ +
++
+
++
Solubility: + +, Soluble at room temperature; +, Soluble on heating; -, Insoluble even on heating

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8052 Jiao et al.
Asian J. Chem.
PDI-Br shows two emission maxima at 554 and 588 nm.
However, PDI-TPA have no fluorescence emission was observed,
possibly due to fluorescence quenching attributed by efficient
intramolecular charge transfer from electron-donating
triphenylamine to electron deficient perylene diimide core19.
Electrochemical properties: The electrochemical
behaviour of perylene diimides has been investigated using
0.1M TBAP as electrolyte at room temperature in dichloro-
methane solutions was depicted in Fig. 4.
It has the potential to be used as electron donating and accep-
ting materials application in OSCs.
ACKNOWLEDGEMENTS
This research was financially supported by the Designed
Project in Innovation Team of Zhejiang Province, China (No.
2011R50001-08), the Natural Science Foundation of Zhejiang
province, China (No. LY12B04001) and the Science and
Technology Planning Project of Jiangbei District, Ningbo City,
Zhejiang province, China (No. 2013A0125). The research was
also supported by the Liu KongAiju Education Fund in Ningbo
University and the K.C. Wong Magna Fund in Ningbo University.
1.19
–0.58
–0.76
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Conclusion
A novel D-A-D perylene diimide derivative PDI-TPA has
been successfully synthesized. PDI-TPA exhibits excellent
solubility in common solvents which is propitious to form film
due to the introduction of the bulky 3-(2-ethylhexoxy)propyl-
amine unit. The absorption bands span a wide range of the
visible spectra and extend to the infrared region, which can
greatly improve the utilization of the solar spectrum. In addi-
tion, PDI-TAP exhibits an ambipolar behaviour, the HOMO
and LUMO energy level are -5.64 and -3.94 eV, respectively.
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