7356 Yi et al.
Asian J. Chem.
Here we report the synthesis, absorption, fluorescence and
J = 6.4 Hz, 2 H), 4.16 (t, J = 5.2 Hz, 4 H), 3.56 (t, J = 5.6 Hz,
4 H), 3.26 (t, J = 5.6 Hz, 4 H), 2.04 (t, J = 6.0 Hz, 4 H), 1.15
(m, 18 H), 0.75 (m, 12 H). Calcd. for C46H52Br2N2O6: C, 62.17;
H, 5.90; N, 3.15. found: C, 62.06; H, 5.98; N, 3.09.
electrochemical behaviour of 1,7-bis-[N,N-bis-(4-methoxy
phenyl)aniline]perylene diimide (PDI2), which use bis-(4-
methoxy-phenyl)phenylamine and 3-(2-ethyl-hexoxy) propyl-
amine attach perylene carboxylic dianhydride (PCD) to bridge
a donor-acceptor-donor configuration of perylene diimide.
4-Bromo-N,N-bis-(4-methoxyphenyl)aniline (5):
4,4'-Dimethoxydiphenylamine (2.05 g, 8.9 mmol), 4-bromo-
iodobenzene (2.97 g, 10.6 mmol) and 1,10-phenanthroline
(0.27 g, 1.5 mmol)were dissolved in toluene (30 mL). After
the solution was heated to 100 ºC, CuCl (0.15 g, 1.5 mmol)
and KOH (1.23 g, 22.0 mmol) were added under N2 purge.
The mixture was refluxed for 48 h at 120 ºC. After being
cooled, the mixture was washed with H2O (50 mL) three
times and the organic phase was dried over Na2SO4. After
removal of the solvent, the residual was purified on a silica
gel column with ethyl acetate:petroleum (v:v, 1:40) as eluent,
yield 46 %. 1H NMR (400 MHz, CDCl3, δ ppm) 7.18 (d, 2 H,
J = 8.0 Hz), 6.56 (d, J = 8.0 Hz, 4 H), 6.36 (d, J = 8.0 Hz, 6
H), 3.40 (s, 6 H).
EXPERIMENTAL
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 spectromete operating at 400
MHz for 1H nucleus, using CDCl3 solvent and TMS as internal
standard, respectively.
The absorbance and fluorescenc spectra were recorded
on a Shimadzu 3101 PC spectrophotometer and Hitachi F-4600
spectrofluorometer, respectively. Dichloromethane solutions
of perylene diimide derivatives in 10×10 mm3 quartz cells were
used for UV-Vis and luminescence measurements.
4-[Bis-(4-methoxyphenyl)amino]phenylboronic acid
(6): To a 50 mL three-necked flask containing the compound
5 (0.86 g, 2.3 mmol) in dried THF (20 mL) equipped with a
magnetic stirrer, a N2 purge and at -78 ºC acetone-dry ice bath
were dropwise added to n-BuLi (2.1 mL, 3.2 mmol, 1.5 M)
while maintaining a good stirring. After stirring for 1 h,
trimethyl borate (0.36 mL, 3.2 mmol) was carefully added.
After stirring at room temperature for another 2 h, water was
first added to the reaction mixture and then HCl (6 M) was
added in a dropwise fashion until an acidic mixture was
obtained. The reaction mixture was poured into water and
extracted with CH2Cl2. The combined organic layer was dried
with anhydrous Mg2SO4 and evaporated to dryness. The crude
product was purified by column chromatography using CH2Cl2
: ethyl acetate (v:v, 10:1) as eluent, yield 47 %. 1H NMR (400
MHz, DMSO-d6, δ ppm): 7.88 (s, 2 H), 7.66 (d, J = 8.0 Hz, 2
H), 7.28 (d, J = 8.0 Hz, 4H), 7.06 (d, 4 H), 6.86 (d, J = 8.0 Hz,
2 H), 3.40 (s, 6 H).
Cyclic voltammograms measurements have been carried
out using 0.1 M tetrabutyl ammonium perchlorate (TBAP) as
supporting electrolyte in dichloromethane 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 synthesized routes of perylene diimides were shown
in Scheme-I. The detailed synthetic procedures are as follows.
1,7-Dibromo-3,4,9,10-perylenetetracarboxylic dianhy-
dride(2): A mixture of 3,4,9,10-perylenetetracarboxylic
dianhydride (20 g, 51.02 mmol) and 300 mL concentrated
sulfuric acid was stirred for 12 h at room temperature and
subsequently I2 (0.48 g, 1.89 mmol) was added. The reaction
mixture was heated to 85 ºC and bromine (5.83 mL, 113.77
mmol) was added dropwise over a time period of 8 h. After
bromine addition, the reaction mixture was heated for an addi-
tional 10 h at 85 ºC and cooled to room temperature. The excess
bromine was removed by a gentle stream of N2 gas and 50 mL
of water was added carefully. The resulting precipitate 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, yield 85 %. IR (KBr, cm-1) 1771, 1739, 1726, 1592,
1376, 1286, 1230, 1166, 1139, 1037, 957, 859, 805, 734, 694.
1,7-Dibromo-N,N'-(3-(2-ethylhexyloxy) propylamine)
-perylenetetracarboxylic acid diimide (PDI1) (3): Com-
pound 2 (2.20 g, 4 mmol), NMP (60 mL), n-butyric acid (40
mL) and 3-(2-ethylhexoxy)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 ºC under N2 purge. After being cooled, the mixture was
poured into 100 mL methanol and stored at temperature of
-10 ºC a 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, yield 70 %. 1H NMR (400 MHz, CDCl3, ppm):
δ 9.37 (d, J = 8.0 Hz, 2 H), 8.83 (s, J = 8.0 Hz, 2 H,), 8.61 (d,
1,7-Bis-[N,N-bis-(4-methoxyphenyl)aniline]-N,N'-bis-
[3-(2-eshylhexyloxy)propylamine]-perylenetetracarboxylic
acid diimide (PDI2) (7): Compound 6 (1.06 g, 1.2 mmol),
compound 6 (0.93 g, 2.7 mmol), Ph(PPh3)4 (0.23 g. 0.2 mmol),
K2CO3 water solution (10 mL, 2 M) and dried toluene (30
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 ºC under N2 purge. After being cooled, the mixture was
poured into 100 mL methanol and stored at temperature of
-10 ºC a 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,
5:1) as eluent, yield 80 %. IR (KBr, νmax, cm-1) 2957, 2925,
2854, 1695, 1654, 1592, 1504, 1408, 1329, 1241, 1178, 1107,
1028, 855, 831, 758, 712; 1H NMR (400 MHz, CDCl3, δ ppm)
8.50 (s, 2 H), 8.14 (d, J = 8.0 Hz, 2 H), 7.98 (d, J = 8.0 Hz, 2
H), 7.23 (d, J = 8.0 Hz, 4 H), 7.08 (d, J = 8.0 Hz, 8 H), 6.87 (d,
J = 8.0 Hz, 4 H), 6.82 (d, J = 8.0 Hz, 8 H), 4.22 (t, J = 6.4 Hz,
4 H), 3.74 (S, 12 H), 3.46 (t, J = 6.0 Hz, 4 H,), 3.20 (t, J = 5.6
Hz, 4 H), 1.94 (m, 4 H), 1.14 (m, 18 H), 0.72 (m, 12 H). Anal.
calcd. for C86H88N4O10: C, 77.22; H, 6.63; N, 4.19. Found: C,
76.95; H, 6.65; N, 4.32.