Facile synthesis and replacement reactions of mono-substituted perylene bisimide dyes

Article abstract of DOI:10.1016/j.dyepig.2012.05.009

Mono-substituted perylene bisimides were synthesized in high yields under mild condition. The starting material was mono-nitrified perylene bisimides instead of usual perylene bisimides halogenated at different levels. Besides phenols and amine, the nucle

Full text of DOI:10.1016/j.dyepig.2012.05.009

Dyes and Pigments 95 (2012) 450e454
Contents lists available at SciVerse ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Facile synthesis and replacement reactions of mono-substituted perylene
bisimide dyes
*
Xiangxue Kong, Juan Gao, Tingting Ma, Ming Wang, Andong Zhang, Zhiqiang Shi , Yanhong Wei
Department of Chemistry, Shandong Normal University, Jinan 250014, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Mono-substituted perylene bisimides were synthesized in high yields under mild condition. The starting
material was mono-nitrified perylene bisimides instead of usual perylene bisimides halogenated at
different levels. Besides phenols and amine, the nucleophilic reagents included alcohol and thiol. The
substitution of nitro group was easier and more effective than the substitution of halogen atoms. But the
substitution reaction of pyrrolidine afforded mono- and 1,6-disubstituted perylene bisimides owing to
the high activity of nitrified perylene bisimides and pyrrolidine. Several replacement reactions between
phenols and alcohol based on phenol mono-substituted perylene bisimide were also found. The
replacement reactions between phenols was fast and in high yield. The absorption of the mono-
substituted perylene bisimides were tunable in the whole visible region.
Received 8 March 2012
Received in revised form
10 May 2012
Accepted 12 May 2012
Available online 19 May 2012
Keywords:
Dye
Perylene bisimide
Substitution reaction
Nitrification
Ó 2012 Elsevier Ltd. All rights reserved.
Replacement reaction
Photophysical property
1. Introduction
derivatives [16e20]. Sometimes the mono-substituted derivatives
need to be designed for special application. However, neither the
Perylene bisimides (PBIs) are important chromospheres in dye
chemistry. In light of their diverse and fascinating properties, such
as excellent electron acceptor ability, high molar extinction coeffi-
cient in the visible region, and high fluorescence quantum yields,
PBI dyes represent a classical example of an inherently robust and
outstandingly versatile family of organic compounds that have
been extensively utilized for a wide range of high technology
applications [1e14]. To meet the demands of various applications,
the electrochemical and photophysical behavior need to be effi-
ciently tuned by functionalization with hydrophobic, hydrophilic
electron-donating or electron-withdrawing groups [15]. The
general strategy for introducing groups onto the PBI core was
substitution reactions or metal-catalyzed cross-coupling reactions
using halogenated PBIs as starting materials. The chlorination or
bromination of PBIs could be readily achieved but resulting in
a mixture of various PBIs halogenated at different levels. The
mixture usually couldn’t be separated by column chromatography
owing to the bad solubilities as well as the presence of
regioisomers. The main products of replacement of the halogen
atoms were di- or tetra- substituted symmetrical perylene
halogenation nor the followed replacement of halogen atoms of
PBIs was facile to be controlled at the first step [21,22]. In addition,
the low activities of halogenated PBIs lead to some reactions are not
easy to be carried out. While the nitrification of PBI can be readily
controlled at the first step owing to the strong electron-
withdrawing effect of nitro group. The mono-nitrated PBI can be
achieved under ambient temperature in a high yield of 90%.
However, the derivativation method of nitrified PBIs has seldom
been investigated. Only a reduction reaction was reported recently
to afford amino-substituted PBI [23]. Herein, a serious substitution
reaction of mono-nitrified PBI were investigated using different
nucleophilic reagents such as phenols, alcohol, thiol and amine.
Several replacement reactions based on phenol mono-substituted
perylene bisimide between phenols and alcohol were found.
2. Experimental
2.1. Materials
All reagents and solvents were of reagent grade quality. All
reagents were obtained from Sinopharm Chemical Reagent Co. Ltd
used as received. All organic solvents employed were obtained
from Beijing Chemical Corporation. Thin-layer chromatography
(TLC) was done on aluminum sheets precoated with Silica 60 F254.
* Corresponding author. Tel.: þ86 531 86182540; fax: þ86 531 82615258.
E-mail address: zshi@sdnu.edu.cn (Z. Shi).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2012.05.009

X. Kong et al. / Dyes and Pigments 95 (2012) 450e454
451
The purification and isolation of the products were performed by
column chromatography on silica gel 60, mesh size 40e63 m or
m. N,N0-dicyclohexyl-3,4:9,10-
and N,N0-dicyclohexyl-1-
2.3.3. Synthesis of 1-ethoxyl-N,N0-dicyclohexyl perylene-3,4:9, 10-
tetracarboxylic diimide (5)
m
silica gel 100, mesh size 63e200
tetracarboxylic acid bisimide
m
1
Method a: Compound 2 (100 mg, 0.17 mmol) and 100 mg K2CO3
were suspended in 6 mL chloroform and 4 mL ethanol. The
mixture was refluxed for 10 h under argon atmosphere. After being
cooled to room temperature, the solution was filtrated and evap-
orated to dryness. The crude product was purified by silica gel
column chromatography with the eluent CH2Cl2/petroleum ether
4:1 to give a red solid 5 (45 mg, 45%). Method b: A mixture of
compound 3 (100 mg, 0.14 mmol) and 100 mg K2CO3 in 4 mL
chloroform and 4 mL ethanol was refluxed for 24 h under argon
atmosphere. The solvent was evaporated under reduced pressure
to give a solid residue. The crude product was washed with MeOH
and then purified by column chromatography on silica gel using
CH2Cl2/petroleum ether 4:1 as the eluent to afford 5 (28 mg, 34%).
nitroperylene-3,4:9,10-tetracarboxylic acid bisimide
synthesized according to the literature procedure [24,25].
2
were
2.2. Equipment
1H NMR and 13C NMR were recorded on Bruker 300 MHz or
600 MHz spectrometers in CDCl3 at room temperature. All chemical
shifts are quoted relative to TMS (
d
¼ 0.0 ppm);
d values are given in
ppm and J values in Hz. Mass spectra were measured on a Bruker
Maxis UHR-TOF MS spectrometer. Electronic absorption spectra
were measured on a Beijing Purkinje General Instrument Co. Ltd.
TU-190 spectrophotometer. The photoluminescence spectra were
recorded on a HITACHI FL-4500 spectrofluorometer.
1H NMR (300 MHz, CDCl3, ppm):
8.63e8.16 (m, 6H), 5.04 (m, 2H), 4.51 (m, 2H), 2.59 (m, 5H),
1.94e1.49 (m, 18H). 13C NMR (75 MHz, CDCl3, ppm):
d
¼ 9.45 (d, 2H, J ¼ 8.2 Hz),
d
¼ 164.43,
163.65, 162.96, 132.33, 130.83, 130.04, 127.63, 126.14, 125.37, 124.41,
124.66, 54.79, 54.23, 53.98, 29.11, 26.52, 25.36. MS (MALDI-TOF):
m/z ¼ 598.25 (Mþ).
2.3. Synthesis
2.3.1. Synthesis of N,N0-dicyclohexyl-1-(4-tert-butylphenoxy)-
perylene-3,4:9,10-tetracarboxylic acid bisimide (3)
2.3.4. Synthesis of 1-propylthio-N,N0-dicyclohexyl perylene-
3,4:9,10-tetracarboxylic diimide (6)
Method a: Compound 2 (200 mg, 0.33 mmol), 4-tert-butyl-
phenol (250 mg, 1.67 mmol), 300 mg K2CO3 and the catalyzed KI
were suspended in 15 mL anhydrous NMP. The reaction mixture
was stirred for 6 h at 25 ꢀC under argon atmosphere. Then MeOH
(10 mL) and 10% HCl solution (50 mL) were added into the
reaction mixture. The precipitate was collected by filtration,
washed with methanol, and then dried in vacuum. The crude
product was further purified by silica gel column chromatography
with the eluent CH2Cl2/petroleum ether 4:1 to give a dark red
solid (210 mg, 90%). Method b: A mixture of N,N0-dicyclohexyl-1-
(4-formoxylphenoxy)-perylene-3,4:9,10-tetracarboxylic acid bisi-
mide 4 (50 mg, 0.074 mmol) and 4-tert-butylphenol (56 mg,
0.37 mmol) in 6 mL anhydrous NMP was stirred for 2 h at 50 ꢀC
under argon atmosphere. After being cooled to room tempera-
ture, MeOH (10 mL) and water (50 mL) was added into the
reaction mixture. The precipitate was collected by filtration,
washed with methanol, and then dried in vacuum. The crude
product was further purified by silica gel column chromatography
with the eluent CH2Cl2/petroleum ether 4:1 to give 3 (47 mg,
Compound 2 (100 mg, 0.17 mmol) and 100 mg K2CO3 were
suspended in 6 mL chloroform and 4 mL n-propyl mercaptan. The
mixture was refluxed for 10 h under argon atmosphere. After
being cooled to room temperature, the solution was filtrated and
evaporated to dryness. The crude product was further purified by
silica gel column chromatography with the eluent CH2Cl2/petro-
leum ether 4:1 to give a red solid 6 (37 mg, 35%). 1H NMR
(300 MHz, CDCl3, ppm):
d
¼ 8.82 (d, 2H, J ¼ 8.0 Hz), 8.65e8.60 (m,
3H), 8.55e8.46 (m, 3H), 5.05 (m, 2H), 3.20e3.15 (m, 2H),
2.61e2.57 (m, 5H), 1.96e1.93 (m, 4H), 1.83e1.75 (m, 6H),
1.52e1.38 (m, 8H), 1.09e1.04 (m, 2H). 13C NMR (75 MHz, CDCl3,
ppm):
d
¼ 163.59, 163.54, 163.43, 139.52, 133.72, 133.41, 132.82,
131.98, 131.03, 130.41, 130.26, 129.21, 128.88, 128.42, 127.29,
126.52, 125.99, 123.19, 123.07, 122.75, 122.02, 121.95, 54.19, 54.03,
37.95, 30.84, 29.15, 26.58, 25.48, 21.92, 13.54. MS (MALDI-TOF): m/
z ¼ 628.24 (Mþ).
2.3.5. Synthesis of 1-pyrrolidinyl-N,N0-dicyclohexyl perylene-
3,4:9,10-tetracarboxylic diimide (7a) and 1,6-dipyrrolidinyl-N,N0-
dicyclohexyl perylene-3,4:9,10-tetracarboxylic diimide (7b)
96%). 1H NMR (600 MHz, CDCl3, TMS):
d
¼ 9.49 (d, 1H, J ¼ 8.4 Hz),
8.60 (m, 5H), 8.24 (s, 1H), 7.48 (d, 2H, J ¼ 7.8 Hz), 7.10 (d, 2H,
J ¼ 7.8 Hz), 5.03 (m, 2H), 2.54 (m, 4H), 1.90 (m, 4H), 1.77 (m, 6H),
1.59e1.46 (m, 6H), 1.39 (s, 9H). 13C NMR (75 MHz, CDCl3, TMS):
Compound 2 (100 mg, 0.17 mmol) in 5 mL pyrrolidine was
stirred at 0 ꢀC for 5 h under argon atmosphere. After the solvent
being evaporated, the solid was purified by silica gel column
chromatography with the eluent CH2Cl2/petroleum ether 2:1 to
give blue solid 7a (32 mg, 30%) and blue-green solid 7b (24 mg,
d
¼ 163.48, 163.30, 162.76, 156.06, 151.83, 148.54, 133.38, 133.30,
132.91, 132.13, 131.28, 130.51, 129.89, 128.87, 128.36, 127.94, 127.71,
127.49, 125.98, 124.89, 124.62, 124.08, 123.46, 123.32, 123.01,
124.31, 123.37, 123.21, 123.12, 122.81, 122.55, 122.03, 121.52,
119.34, 54.58, 54.21, 54.02, 34.55, 31.43, 29.09, 26.59, 25.50. MS
(MALDI-TOF): m/z ¼ 702.33 (Mþ).
20%). 7a: 1H NMR (300 MHz, CDCl3, ppm):
J ¼ 8.0 Hz), 8.47e8.52 (m, 4H), 7.53 (d, 2H, J ¼ 8.0 Hz), 5.09 (m,
2H), 3.79 (m, 2H), 2.79 (m, 2H), 2.65e2.57 (m, 4H), 2.13 (m, 2H),
1.96e1.92 (m, 4H), 1.81e1.78 (m, 6H), 1.52e1.38 (m, 6H). 13C NMR
d
¼ 8.64 (d, 2H,
2.3.2. Synthesis of N,N0-dicyclohexyl-1-(4-formaldehyde phenoxy)-
perylene-3,4:9,10-tetracarboxylic acid bisimide (4)
Compound 4 was synthesized as the procedure of synthesis of 3.
100 mg compound 2 and 100 mg 4-hydroxy-benzaldehyde reacted
for 6 h in NMP to yield 4 in 92%. 1H NMR (300 MHz, CDCl3, ppm):
(75 MHz, CDCl3, ppm):
d
¼ 164.31, 164.24, 164.13, 148.42, 135.19,
134.93, 132.51, 130.90, 130.65, 128.94, 127.07, 126.58, 124.18,
123.57, 123.11, 122.83, 122.57, 122.14, 120.38, 119.53, 115.96, 53.99,
53.75, 52.24, 29.68, 29.18, 29.10, 26.60, 25.72, 25.50. MS (MALDI-
TOF): m/z ¼ 623.28 (Mþ). 7b: 1H NMR (300 MHz, CDCl3, ppm):
d
¼ 9.99 (s, 1H), 9.34 (d, 2H, J ¼ 8.3 Hz), 8.67 (m, 4H), 8.57 (d, 2H,
d
¼ 8.65 (d, 2H, J ¼ 8.0 Hz), 8.33 (s, 2H), 7.90 (d, 2H, J ¼ 8.0 Hz),
J ¼ 8.3 Hz), 8.27 (s, 1H), 7.96 (d, 2H, J ¼ 8.6 Hz), 7.20 (d, 2H,
J ¼ 8.6 Hz), 5.02 (m, 2H), 2.53 (m, 4H), 1.92 (m, 4H), 1.55e1.28 (m,
5.13e5.04 (m, 2H), 3.71 (m, 4H), 2.67e2.56 (m, 8H), 2.01e1.90 (m,
12H), 1.76 (m, 6H), 1.27e1.51 (m, 6H). 13C NMR (75 MHz, CDCl3,
8H). 13C NMR (75 MHz, CDCl3, ppm):
d
¼ 190.39, 163.64, 163.63,
ppm):
d
¼ 160.10, 159.85, 145.27, 130.76, 126.26, 125.40, 123.70,
162.88, 160.11, 153.78, 132.22, 131.84, 128.69, 126.03, 122.71, 118.81,
110.02, 54.01, 53.43, 29.10, 29.07, 26.52, 26.48, 25.42, 25.39. MS
(MALDI-TOF): m/z ¼ 674.24 (Mþ).
123.55, 118.60, 118.56, 113.62, 112.85, 112.46, 112.22, 49.20, 48.80,
47.30, 24.48, 24.38, 21.89, 21.83, 20.87. MS (MALDI-TOF): m/
z ¼ 692.34 (Mþ).

452
X. Kong et al. / Dyes and Pigments 95 (2012) 450e454
3. Results and discussions
3.1. Synthesis
The chemical structures of compounds 1-7a and their synthetic
routes are shown in Scheme 1. The synthesis started from an
imidization of perylene bisanhydride by reaction with cyclohexyl-
amine. The mono-nitrated perylene-3,4:9,10-tetracarboxylic bisi-
mide 2 was achieved by a reaction of perylene bisimides 1 with
cerium (IV) ammonium nitrate (CAN) and HNO3 under ambient
temperature in a high yield. The substitutions of nitro group of 2
with 4-tert-butylphenoxy, ethoxyl, propylthio and pyrrolidinyl
group were performed in different solvents to obtain the corre-
sponding substituted products 3-7. By exchange of phenols or
ethanol, compound 3 could be prepared from compound 4 and
could also be used to prepare compound 5. The replacement
reactions are summarized in Scheme 2.
Scheme 2. The replacement reactions between 3, 4, 5.
bromized PBI reacting over 100ꢀC [26], the substitution of nitro
group by 4-tert-butylphenoxy group took place quickly at room
temperature. Catalyzed by KI, the reaction time could be shortened
from 10 h to 6 h. Almost without any byproduct, the product was
pure enough to be used in other reactions just through precipita-
tion from the resulting solution by adding methanol and HCl
solution and then being washed with methanol. Compound 4 was
synthesized as the procedure of synthesis of 3 using 4-hydroxy-
benzaldehyde as phenol. Besides phenols, alcohol and thiol could
react with mono-nitrified PBI in chloroform to yield corresponding
substituted products. This kind of reaction has seldom been re-
ported for halogenated PBI owing to its lower activity than nitrified
PBI [27].
Generally the substitution reaction of bromized PBIs with pyr-
rolidine take place at original position, i.e. the bromine atoms are
replaced by pyrrolidinyl groups [23,28,29]. Similar as the bromized
PBIs, mono-nitrified PBI 2 could react with pyrrolidine. But beside
the mono-substituted product of 7a, 1,6-disubstituted PBI 7b was
also obtained. When the reaction was carried out under 25 ꢀC, 7a
was the major product. Otherwise 7b was the major product.
Besides the substitution reactions of halogenated or nitrified
PBIs, the replacement reactions of phenol substituted PBIs were
noted. Compound 4 could react with 4-tert-butylphenol in NMP to
give compound 3 in high yield. However compound 4 couldn’t be
prepared from 3. Similarly compound 3 could react with ethanol in
chloroform to give compound 5. But compound 3 couldn’t be
prepared from 5. A reaction mechanism of those replacement
reactions was proposed that a weaker nucleophile could be
substituted by a stronger nucleophile to form new OeC bond.
1-nitro-N,N0-dicyclohexyl perylene-3,4:9,10-tetracarboxylic bisi
mide 2 was synthesized by the reaction of N,N0-dicyclohexyl per-
ylene-3,4:9,10-tetracarboxylic bisimide with 96% nitric acid and
Ce(NH4)2(NO3)6 in CH2Cl2 with a high yield of more than 90%.
Usually, the bromination of perylene bisimide 1 resulted in main
products of regioisomers of dibrominated PBIs and low ratio of
mono- as well as tri-brominated PBIs. Compared with the bromi-
nation of PBIs, the nitrification of PBI was readily to be controlled at
first step due to the far stronger electron-withdrawing effect of
nitro group than bromine atom. In addition, the mono-nitrified PBI
has a good solubility in organic solvent thus its purification is easy.
The substitution reactions of nitrified PBI could be carried out
smoothly with phenols in high yields. The yields of substitution
reactions of compound 2 with 4-tert-butylphenol in different
solvents were compared. The reaction proceeded entirely in N-
methyl-2-pyrrolidone (NMP) with a yield of ca 90%. However, in
DMF or CHCl3, the yields of the reactions under the same condition
were less than 65%. Compared with the similar reaction of mono-
Scheme 1. The synthesis of compounds 3-7a.
Fig. 1. Absorption spectra of compound 1-7 in chloroform (10ꢁ5 M).

X. Kong et al. / Dyes and Pigments 95 (2012) 450e454
453
Table 1
Absorption data for 1-7 in chloroform (10ꢁ5 M).
Compound
1
2
3
4
5
6
7a
7b
682.0
3.16
lmax (nm)
525.5
521.5
538.5
525.5
520.5
545.5
644.0
3
(104 Mꢁ1 cmꢁ1
)
7.87
3.10
3.47
4.11
4.26
3.29
3.13
3.2. Absorption properties of dyes
compounds 3 and 4, alkyl substituted compounds 5 and 6 show
weaker emission. Incorporated with strong electron-withdrawing
group of nitryl and electron-donating groups of pyrrolidinyl,
compound 2, 7a and 7b exhibit very weak emission.
The UVevis absorption spectra of the compounds in chloroform
at room temperature are shown in Fig. 1 and the absorption data
are given in Table 1. All of the compounds show intense absorption
in the visible region. Compound 1 shows strong PBI core absorption
band at 526 nm. Compared with compound 1, a slight blue-shift
about 4 nm in the absorption of 2 is observed. The phenomenon
may be attributed to the decrease of molecular rigidity due to the
enhanced steric hindrance induced by the nitro group. The
maximal absorption bands of compound 3 and 4 red-shift about 17
and 4 nm respectively compared with that of 2. Because the
introduction of phenoxy group at the bay position has enlarged the
conjugation system of PBI core. The longest wavelength absorption
band of 5 and 6 appear at 553 and 544 nm respectively. Notably,
introduction of electron-donating groups of pyrrolidinyl groups
induces remarkable red-shifts and the pyrrolidinyl-substituted
compounds 7a and 7b display large differences in their absorptive
features compared with 2. The maximum absorption of 7a appears
at 643 nm. The lowest energy band is highly red-shifted with
respect that of nitro-substituted PBI 2, reflecting pronounced
electronic interaction between PBI core and pyrrolidinyl groups. In
addition, it also exhibits a higher energy electronic transition at
430 nm. Compared with compound 7a, the lowest energy band has
a longer red-shift about 38 nm for 7b. In addition, a shoulder peak
shows as strong as the maximal absorption band and an additional
strong band appears at 563 nm. Due to the compound 7a and 7b
cover a large region of the visible light, the compounds may be used
as special dyes in solar cell.
4. Conclusions
In conclusion, the substitution reactions of mono-nitrified per-
ylene bisimides have been investigated. Besides phenols, alcohol
and thiol could carry out the substitution reaction. For pyrrolidine,
both mono and 1,6-disubstituted PBIs were obtained. The pyrroli-
dinyl substituted PBIs show intense and broad absorption in the
visible region. In addition, several replacement reactions between
phenols and alcohol based on phenol mono-substituted perylene
bisimide have been developed.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (20771067).
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