Synthesis of water-soluble perylene dicarboximide derivatives containing pyridine oxide groups

Article abstract of DOI:10.1080/00397911.2010.540731

Several water-soluble perylene dicarboximide derivatives were synthesized by indroducing pyridine oxide moieties to the perylene core or to imide groups. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397911.2010.540731

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Synthesis of Water-Soluble Perylene
Dicarboximide Derivatives Containing
Pyridine Oxide Groups
Juanjuan Sun a , Ming Wang a , Ping Xu a , Shuai Zhang a & Zhiqiang
Shi a
a Department of Chemistry, Shandong Normal University, Jinan, P. R.
China
Accepted author version posted online: 21 Oct 2011.Version of
record first published: 25 Jan 2012.
To cite this article: Juanjuan Sun , Ming Wang , Ping Xu , Shuai Zhang & Zhiqiang Shi (2012): Synthesis
of Water-Soluble Perylene Dicarboximide Derivatives Containing Pyridine Oxide Groups, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
42:10, 1472-1479
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Synthetic Communications1, 42: 1472–1479, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.540731
SYNTHESIS OF WATER-SOLUBLE PERYLENE
DICARBOXIMIDE DERIVATIVES CONTAINING
PYRIDINE OXIDE GROUPS
Juanjuan Sun, Ming Wang, Ping Xu, Shuai Zhang, and
Zhiqiang Shi
Department of Chemistry, Shandong Normal University, Jinan,
P. R. China
GRAPHICAL ABSTRACT
Abstract Several water-soluble perylene dicarboximide derivatives were synthesized by
indroducing pyridine oxide moieties to the perylene core or to imide groups.
Keywords Fluorescence; perylene diimides; pyridine-N-oxide; water-soluble chromophore
INTRODUCTION
Although there are a large variety of water-soluble chromophores commer-
cially available today, most of them exhibit relatively low fluorescence quantum
yields and=or photochemical stabilities.[1,2] Perylene diimides (PDI) derivative is
one outstandingly versatile organic chromophore.[3–6] PDI demonstrates exceptional
thermal and photochemical stability, strongly absorbs visilble light, and shows high
fluorescence quantum yield.[7,8] Because of the unique properties of PDI, it plays an
important role in diverse fields such as biological applications,[9,10] where water solu-
bility is an essential issue. Most PDI derivatives exhibit high fluorescence and good
Received January 7, 2010.
Address correspondence to Zhiqiang Shi, Department of Chemistry, Shandong Normal University,
Wenhuadonglu Road, Jinan 250014, China. E-mail: zshi@sdnu.edu.cn
1472

WATER-SOLUBLE PERYLENE DICARBOXIMIDE DERIVATIVES
1473
solubility in organic solvents but poor water solubility and very weak fluorescence in
water because of aggregation of the perylene core.[11–13] Until now, only a few
water-soluble PDI derivatives have been reported with hydrophilizing substituents,
such as quaternized amine groups,[11] sulfonic acid moieties,[12] crown ethers[13] as
part of the imide structure of the chromophore, polyethylene glycol,[14] or peptide
chains[15] attached to the chromophore scaffold. In all cases these perylene chromo-
phores show almost no fluorescence in water. Herein, several pyridine N-oxide
groups were attached to the aromatic chromophore, which shown high fluorescence
and good water solubility.
RESULTS AND DISCUSSION
As we all know, the perylene core is rich in negative charge due to the
p-stacking and results in aggregation behavior of perylene chromophores. There
are two strategies to solve the solubility of perylene in water. One method introduces
a hydrophilic group on the perylene, which can simultaneously twist the perylene
core, and the group is like dendritic wedges that effectively shield the chromophores
to suppress the effects of aggregation of the perylene, and the perylene core dispersed
in water. However, the number of hydrophilic groups is not as much as we can pre-
dict. The other method, electron acceptors or positive group attached to the perylene
core, could transfer the charge of perylene core itself, hence decreasing the degree
of aggregation of perylene. Based on this concept, the synthesis of PDIs with one
pyridine N-oxide substituent attached at the bay region was accomplished through
treatment of (N,N0-dicyclohexyl-1-bromo)perylene-3,4:9,10-tetracarboxydiimide,
which is available on a gram scale, with 3 equivalents of 3-hydroxypyridine in
1-methyl-2-pyrrolidone (NMP) (80% yield, Scheme 1). Because this chromophore
Scheme 1. Synthesis of compounds 3 and 6.

1474
J. SUN ET AL.
Scheme 2. Synthesis of the compound 10.
Scheme 3. Synthesis of the compound 12.

WATER-SOLUBLE PERYLENE DICARBOXIMIDE DERIVATIVES
1475
is not soluble in water, N,N0-dicyclohexyl-1-(3-pyridine-N-oxide)perylene-3,4:9,10-
tetracarboxylic acid bisimide 3 was prepared by oxidation of N,N0-dicyclohexyl-
1-(3-pyridoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide 2 with H2O2 in
CH3COOH (54% yield). The synthesis of the two pyridine N-oxide-substituted
PDI chromophores involved phenoxylation with 3-pyridinol by the same procedure
as described previously, to yield N,N0-Dicyclohexyl-1,7-di(3-pyridine-N-oxide)-
perylene-3,4:9,10-tetracarboxylic acid bisimide 6 (45% yield).
The N,N0-di(4-pyridine-N-oxide)-1,7-di(4-tert-butylphenoxy)perylene-3,4:9,10-
tetracarboxylic acid bisimide 10 was derived from (N,N0-dicyclohexyl-1,7-
dibromo)perylene-3,4:9,10-tetracarboxydiimide 4 in four steps via aryloxylation,
saponification, imidation, and oxidation (Scheme 2). The purposed compound 12
was achieved by the means of oxidizing of compound 11[16] with H2O2 in CH3COOH
(58% yield, Scheme 3).
CONCLUSION
In summary, facile synthesis routes of a kind of water-soluble chromophore
based on PDI have been developed by indroducing pyridine oxide moieties to a per-
ylene core or imide groups. This strategy results in good solubility in water and high
fluorescence.
EXPERIMENTAL
N,N’-Dicyclohexyl-1-(3-pyridoxy)perylene-3,4:9,10-tetracarboxylic acid
bisimide 2. Compound 1 (0.50 g, 0.79 mmol), K2CO3 (0.49 g, 3.55 mmol), and
3-hydroxypyridine (0.30 g, 3.16 mmol) were dissolved in N-methyl-2-pyrrolidone
(15 mL). The solution was stirred at 80 ꢀC under argon for 13 h. The reaction mixture
was chilled to room temperature, and aqueous HCl solution (2 N) was added. The
solution was filtered, and the precipitate was washed with water. The red solid
was dried at 50 ꢀC under vacuum overnight. The product was purified by column
chromatography over silica gel (CH2Cl2–acetone ¼ 50:1) to yield a red solid
1
(409 mg, 80%). H NMR (300 MHz, CDCl3, ppm) d 1.32–1.44 (m, 7H), 1.76 (m,
5H), 1.92 (m, 4H), 2.54 (m, 4H), 5.00 (m, 1H), 5.04 (m, 1H), 7.49–7.55 (m, 2H),
8.22 (s, 1H), 8.55–8.72 (m, 7H), 9.39 (d, 1H, J ¼ 8.3 Hz). 13C NMR (75 MHz, CDCl3,
ppm): d 25.42, 26.52, 29.10, 54.04, 54.22, 122.70, 123.61, 123.80, 124.49, 125.25,
126.32, 126.87, 127.48, 128.47, 128.60, 129.07, 130.39, 130.94, 131.78, 132.89,
134.03, 134.46, 140.19, 152.23, 154.32, 162.82, 163.57, 163.63, 163.88. MS (MALDI):
647 (Mþ).
N,N’-Dicyclohexyl-1-(3-pyridine-N-oxide)perylene-3,4:9,10-tetracarboxylic
acid bisimide 3. Compound 2 (0.3 g, 0.46 mmol) were dissolved in CH3COOH
(8 mL), and 0.5 mL H2O2 was added. The solution was stirred at room temperature
for half an hour, and the temperature rose to 80 ꢀC. About 3 h later, 0.5 mL H2O2
was added again, and the mixture continued to stir for 20 h. The reaction mixture
was chilled to room temperature, and water was added. The solution was filtered,
and the precipitate was washed with water. The red solid was dried at 50 ꢀC under
vacuum overnight. The product was purified by column chromatography over silica

1476
J. SUN ET AL.
gel (CHCl3–THF–methanol ¼ 250:50:3) to yield a red solid (166 mg, 54%). 1H NMR
(300 MHz, CDCl3, ppm) d 1.37–1.51 (m, 6H), 1.78–1.91 (m, 10H), 2.52–2.60 (m,
4H), 5.04 (m, 2H), 7.45 (m, 1H), 8.23 (m, 2H), 8.31 (s, 1H), 8.63 (d, 1H, J ¼ 7.6 Hz),
8.68–8.74 (m, 5H), 9.21 (d, 2H, J ¼ 7.6 Hz). 13C NMR (75 MHz, CDCl3, ppm): d
25.39, 26.49, 29.08, 29.29, 29.67, 54.09, 54.29, 116.10, 122.95, 123.61, 123.95,
125.47, 126.30, 126.82, 127.91, 128.39, 129.05, 130.83, 131.04, 131.69, 132.29,
133.80, 134.56, 135.76, 141.59, 152.48, 154.40, 162.62, 163.44, 163.50, 163.77. MS
(MALDI): 663 (Mþ). Anal. calc. for C41H33N3O6: C, 74.19; H, 5.01; N, 6.33. Found:
C, 73.98; H, 4.89; N, 6.20.
N,N’-Dicyclohexyl-1,7-di(3-pyridoxy)perylene-3,4:9,10-tetracarboxylic
acid bisimide 5. Compound 4 (0.50 g, 0.70 mmol), K2CO3 (0.49 g, 3.50 mmol), and
3-hydroxypyridine (0.34 g, 3.58 mmol) were dissolved in 1-methyl-2-pyrrolidone
(15 mL). The solution was stirred at 80 ꢀC under argon for 15 h. The reaction mixture
was chilled to room temperature, and aqueous HCl solution (2 N) was added. The
solution was filtered, and the precipitate was washed with water. The red solid
was dried at 50 ꢀC under vacuum overnight. The product was purified by column
chromatography over silica gel (CH2Cl2–acetone ¼ 20:1) to yield a red solid
1
(414 mg, 80%). H NMR (300 MHz, CDCl3, ppm) d 1.25–1.45 (m, 8H), 1.61–1.91
(m, 8H), 2.44–2.52 (m, 4H), 4.96 (m, 2H), 7.40–7.48 (m, 4H), 8.26 (s, 2H), 8.54
(m, 4H), 8.64 (d, 2H, J ¼ 8.3 Hz), 9.47 (d, 2H, J ¼ 8.3 Hz). 13C NMR (75 MHz,
CDCl3, ppm): d 25.36, 26.46, 29.06, 54.21, 123.22, 123.91, 124.19, 124.95, 125.62,
126.73, 127.91, 129.07, 130.52, 131.06, 132.61, 153.94, 162.82, 163.34. MS (MALDI):
740 (Mþ).
N,N’-Dicyclohexyl-1,7-di(3-pyridine-N-oxide)perylene-3,4:9,10-tetra-
carboxylic acid bisimide 6. Compound 5 (0.30 g, 0.40 mmol) were dissolved in
CH3COOH (8 mL), and 0.5 mL H2O2 was added. The solution was stirred at room
temperature for half an hour, and the temperature rose to 80 ꢀC. About 3 h later,
0.5 mL H2O2 was added again, and the mixture continued to stir for 24 h. The reac-
tion mixture was chilled to room temperature, and water was added. The solution
was filtered, and the precipitate was washed with water. The red solid was dried at
50 ꢀC under vacuum overnight. The product was purified by column chromato-
graphy over silica gel (CH2Cl2–methanol ¼ 100:2) to yield a red solid (140 mg,
1
45%). H NMR (300 MHz, CDCl3, ppm) d 1.25–1.51 (m, 8H), 1.63–1.92 (m, 8H),
2.48–2.53 (m, 4H), 4.98 (m, 2H), 7.13–7.37 (m, 4H), 8.12 (m, 4H), 8.36 (s, 2H),
8.65 (d, 2H, J ¼ 8.3 Hz), 9.29 (d, 2H, J ¼ 8.3 Hz). 13C NMR (75 MHz, CDCl3,
ppm): d 23.90, 25.33, 26.43, 29.02, 54.31, 67.60, 107.87, 116.47, 123.65, 125.05,
125.16, 125.47, 126.37, 129.05, 131.07, 131.20, 132.12, 152.11, 162.56, 163.14. MS
(MALDI): 770 (Mþ). Anal. calc. for C46H36N4O8: C, 71.49; H, 4.70; N, 7.25. Found:
C, 71.12; H, 4.56; N, 7.16.
N,N’-Dicyclohexyl-1,7-di(4-tert-butylphenoxy)perylene-3,4:9,10-tetra-
carboxydiimide 7. Compound 4 (1.00 g, 1.40 mmol), K2CO3 (0.97 g, 7.03 mmol),
and 4-tert-butylphenol (0.87 g, 5.80 mmol) were dissolved in 1-methyl-2-pyrrolidone
(NMP) (30 mL). The solution was stirred at 80 ꢀC under argon for 18 h. The mixture
was chilled to room temperature, and aqueous HCl solution (2 N) was added. The
solution was filtered, and the precipitate was washed with water. The red solid

WATER-SOLUBLE PERYLENE DICARBOXIMIDE DERIVATIVES
1477
was dried at 50 ꢀC under vacuum overnight. The product was purified by column
chromatography over silica gel (CH2Cl2–petroleum ether ¼ 1:1) to yield a red solid
1
(1.01 g, 85%). H NMR (300 MHz, CDCl3, ppm) d 1.18 (m, 6H), 1.28 (s, 18H),
1.60 (m, 6H), 1.75 (m, 4H), 2.53 (m, 4H), 5.01 (m, 2H), 7.10 (d, 4H, J ¼ 8.2 Hz),
7.48 (d, 4H, J ¼ 8.2 Hz), 8.29 (s, 2H), 8.53 (d, 2H, J ¼ 8.3 Hz), 9.54 (d, 2H,
J ¼ 8.3 Hz).13C NMR (75 MHz, CDCl3, ppm) : d 25.44, 26.52, 29.10, 29.68, 31.46,
31.92, 34.53, 54.02, 119.23, 122.55, 123.35, 123.54, 124.15, 124.88, 127.41, 128.61,
128.96, 129.94, 133.15, 148.10, 152.53, 155.36, 163.30, 163.67. MS (MALDI):
850 (Mþ).
N,N’-Di(4-pyridyl)-1,7-di(4-tert-butylphenoxy)perylene-3,4:9,10-tetra-
carboxylic acid bisimide 9. Compound 7 (0.50 g, 0.59 mmol) was added to
4-tert-butanol (30 mL), potassium hydroxide (1.65 g, 29.50 mmol), and water
(2.6 mL), and the resulting solution was refluxed for 25 h. Then the crude mixture
was cooled to room temperature, and aqueous HCl solution (2 M) and water were
added. The solution was filtered, and the precipitate was washed with water and
dried. The product 8 was not handled further as the next step’s materials.
A mixture of compound 8 (0.4 g, 0.58 mmol), 4-aminopyridine (0.19 g,
2.02 mmol), and zinc acetate (0.10 g, 0.45 mmol) in quinoline (20 mL) was stirred under
argon at 180 ꢀC for 20 h. After the solution was chilled, 2 M hydrochloric acid (150 mL)
was added to precipitate the product, which was collected by suction filtration, washed
thoroughly with a large amount of water and methanol and dried in a vacuum. The
crude product was purified by column chromatography silica gel (CH2Cl2–
1
THF ¼ 50:1) to yield a dark purple powder (341 mg, 70%). H NMR (300 MHz,
CDCl3, ppm) d 1.37 (s, 18H), 7.13 (d, 4H, J ¼ 7.8 Hz), 7.47 (d, 4H, J ¼ 7.8 Hz), 7.50
(d, 4H, J ¼ 7.1 Hz), 8.41 (s, 2H), 8.69 (d, 2H, J ¼ 8.4 Hz), 8.86 (d, 4H, J ¼ 7.1 Hz),
9.73 (d, 2H, J ¼ 8.4 Hz). 13C NMR (75 MHz, CDCl3, ppm): d 31.41, 34.61, 119.36,
121.36, 122.73, 123.22, 123.81, 124.55, 125.59, 127.68, 128.07, 128.89, 131.33,
132.04, 134.42, 149.00, 152.06, 157.15, 161.92, 162.60. MS (MALDI): 841 (Mþ).
N,N’-Di(4-pyridine-N-oxide)-1,7-di(4-tert-butylphenoxy)perylene-3,4:9,10-
tetracarboxylic acid bisimide 10. Compound 9 (0.25 g, 0.30 mmol) were dissolved
in CH3COOH (6 mL), and 0.5 mL H2O2 was added. The solution was stirred at room
temperature for half an hour, and the temperature rose to 80 ꢀC. About 3 h later,
0.5 mL H2O2 was added again and stirred for 20 h. The reaction mixture was chilled
to room temperature, and water was added. The solution was filtered, and the
precipitate was washed with water. The red solid was dried at 50 ꢀC under vacuum
overnight. The product was purified by column chromatography over silica gel
(CHCl3–THF–CH3OH ¼ 100:10:3) to yield a red solid (143 mg, 55%). 1H NMR
(300 MHz, CDCl3, ppm) d 1.38 (s, 18H), 7.14 (d, 4H, J ¼ 8.4 Hz), 7.51 (d, 4H,
J ¼ 8.4 Hz), 7.63 (d, 4H, J ¼ 7.2 Hz), 8.44 (s, 2H), 8.71 (d, 2H, J ¼ 8.5 Hz), 8.75 (d,
4H, J ¼ 7.2 Hz), 9.74 (d, 2H, J ¼ 8.5 Hz); 13C NMR (75 MHz, CDCl3, ppm): d
31.41, 34.62, 119.21, 121.44, 123.01, 124.14, 124.98, 127.70, 129.19, 130.77, 134.03,
139.96, 148.99, 152.11, 155.98, 162.08, 162.38. MS (MALDI): 872 (Mþ). Anal. calc.
for C54H40N4O8: C, 74.30; H, 4.62; N, 6.42. Found: C, 74.18; H, 4.55; N, 6.31.
N,N’-Di(4-pyridine-N-oxide)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,
4:9,10-tetracarboxylic acid bisimide 12. Compound 11[16] (0.25 g, 0.22 mmol)

1478
J. SUN ET AL.
Table 1. Solubility in H2O and UV-visible absorption and fluorescence emission spectral data of 10ꢁ5 M
perylene dicarboximide derivatives containing pyridine oxide groups in 20% THF=H2O (v=v)
Compound
Solubility (M)
UV-vis (kmax
)
Emission (kEx=kEm
)
Quantum yields (U)
3
6
4 ꢂ 10ꢁ5
479
540
490
602
526=551
529=566
545=567
584=617
0.31
0.48
0.35
0.22
10ꢁ4
10
12
2 ꢂ 10ꢁ5
8 ꢂ 10ꢁ6
was dissolved in CH3COOH (6 mL), and 0.5 mL H2O2 was added. The solution was
stirred at room temperature for half an hour, and the temperature rose to 80 ꢀC.
About 3 h later, 0.5 mL H2O2 was added again, and the mixture continued to stir
for 20 h. The reaction mixture was chilled to room temperature, and water was
added. The solution was filtered, and the precipitate was washed with water. The
red solid was dried at 50 ꢀC under vacuum overnight. The product was purified by
column chromatography over silica gel (CH2Cl2–THF–methanol ¼ 250:50:3) to yield
1
a red solid (150 mg, 58%). H NMR (300 MHz, CDCl3, ppm) 1.29 (s, 36H), 6.84 (d,
8H, J ¼ 8.3 Hz), 7.26 (d, 8H, J ¼ 8.3 Hz), 7.58 (d, 4H, J ¼ 6.3 Hz), 8.26 (s, 4H), 8.71
(d, 4H, J ¼ 6.3 Hz). 13C NMR (75 MHz, CDCl3, ppm): d 31.39, 34.41, 119.25, 119.50,
120.31, 121.18, 121.58, 126.85, 127.24, 133.13, 139.72, 147.95, 152.46, 156.28, 162.38.
MS (MALDI): 1168 (Mþ). Anal. calc. for C74H64N4O10: C, 76.01; H, 5.52; N, 4.79.
Found: C, 75.92; H, 5.46; N, 4.71.
All of the perylene dicarboximide derivatives containing pyridine oxide groups
are soluble in water. As shown in Table 1, the water solubility of the compounds 3
and 6 with pyridine oxide groups incorporated at the bay positions is better than that
of the compounds 10 and 12 incorporating pyridine oxide groups at the imide nitro-
gens. The number of pyridine oxide groups improves the water solubility, whereas
the number of phenol groups reduces the water solubility. The solubility increases
significantly in a mixture of solvents H2O=THF or H2O=EtOH. Ultraviolet-visible
absorption and fluorescence emission intensity also increase obviously before the
THF up to 30% (v=v) in the mixture of solvents and then change slowly. UV-visible
absorption and fluorescence emission spectral data of compounds 3, 6, 10, and 12 in
20% THF=H2O (v=v) are listed in Table 1. The data indicate the quantum yields
increase with the solubilites.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of
China (20771067) and the Natural Science Foundation of Shandong Province
(2008BS02004).
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