Self-Assemblies of Perylene Bisimide Dyes
acid and then water. The organic layer was separated and
subsequently dried over Na2SO4 and concentrated under vacuum.
Purification of the residue by silica gel column chromatography
(2.5% MeOH in CHCl3 as an eluent) and reprecipitation from the
MeOH-CHCl3 mixture gave MPBI2 as a red solid (183 mg, 68%
yield): 1H NMR (500 MHz, 1,1,2,2-tetrachloroethane-d2, 90 °C) δ
) 8.54 (m, J ) 8.0 Hz, 4H), 8.42 (m, J ) 8.0 Hz, 4H), 6.68 (s,
4H), 4.43 (m, J ) 6.5 Hz, 4H), 3.83 (m, 16H), 3.42 (m, 8H), 1.64
(m, 20H), 1.28 (m, 148H), 0.85 (t, 30H); 13C NMR (125 MHz,
1,1,2,2-tetrachloroethane-d2, 90 °C) δ ) 164.8, 154.4, 135.9, 132.7,
130.7, 127.8, 124.5, 124.4, 101.8, 70.9, 48.6, 44.8, 41.5, 413, 33.2,
33.1, 31.7, 31.0, 30.9, 30.8, 30.6, 30.5, 29.3, 28.3, 27.5, 23.9, 15.3.
MS (MALDI-TOF) calcd for C150H242N14O10Na (m/z) 2424.6 [M
+ Na]+, found 2423.9. Anal. Calcd for C150H242N14O10 ·2H2O: C,
73.91; H, 10.17; N, 8.04. Found: C, 73.94; H, 10.16; N, 8.09.
N,N′-Bis[3-{4-dioctylamino-6-(3,4,5-tris-dodecyloxy-phenyl)-
amino-[1,3,5]triazin-2-ylamino}-propyl]perylene-3,4:9,10-tetra-
carboxylic Acid Bisimide (MPBI3): Perylene-3,4:9,10-tetracar-
boxylic acid bisanhydride (40 mg, 0.10 mmol), compound 2 (290
mg, 0.280 mmol), zinc acetate (39 mg), and imidazole (3.1 g) were
refluxed under nitrogen for 7 h. After cooling to room temperature,
the mixture was dissolved in CHCl3 and washed with 2 M
hydrochloric acid and then water. The organic layer was separated
and subsequently dried over Na2SO4 and concentrated under
vacuum. Purification of the residue by silica gel column chroma-
tography (3% MeOH in CHCl3) and reprecipitation from the
CHCl3-MeOH mixture gave MPBI3 as a red solid (132 mg, 53%
yield): 1H NMR (500 MHz, 1,1,2,2-tetrachloroethane-d2, 90 °C) δ
) 8.63 (m, J ) 8.0 Hz, 4H), 8.53 (m, J ) 8.0 Hz, 4H), 6.76 (s,
4H), 4.29 (t, J ) 6.5 Hz, 4H), 3.87 (m, 16H), 3.48 (m, 8H), 2.08
(m, 4H), 1.80 (m, 20H), 1.30 (m, 148H), 0.85 (t, 30H); 13C NMR
(125 MHz, 1,1,2,2-tetrachloroethane-d2, 90 °C) δ ) 162.9, 152.6,
134.2, 130.9, 128.9, 126.0 122.7, 122.6, 101.5, 69.0, 47.0, 43.9,
42.0, 41.8, 38.0, 31.2, 31.1, 29.8, 29.1, 29.0, 28.8, 28.6, 28.5, 27.4,
Experimental Section
MPBI2 and MPBI3 were prepared according to Scheme 1. The
synthesis of cCA will be reported elsewhere. 3,4,5-Tri(dodecy-
loxy)aniline was prepared according to a literature method.45
2-Chloro-4-dioctylamino-6-{(3,4,5-tridodecyloxyphenyl)amino}-
[1,3,5]triazine (4): 442 mg of 3,4,5-tri(dodecyloxy)aniline (0.684
mmol) in 10 mL of dry THF was added to a dry THF solution (50
mL) of 126 mg of 1,3,5-trichloro-s-triazine (0.689 mmol) and 2.0
mL of diisopropylethylamine (DIPEA) at room temperature, and
the mixture was stirred for 2 h. Additional DIPEA (1.5 mL) and
170 mg of dioctylamine (0.705 mmol) were added dropwise. After
stirring for 2.5 h at room temperature, solvent was evaporated, and
the residue was dissolved in an appropriate amount of CHCl3. The
resulting solution was washed with 2 M hydrochloric acid and then
water, and the separated organic phase was dried over Na2SO4.
After the solvent was evaporated, the residue was purified by silica
gel column chromatography (10% AcOEt in hexane) to give 4 (490
1
mg, 71% yield): H NMR (400 MHz, CDCl3) δ ) 6.75 (s, 2H),
3.95 (m, 6H), 3.52 (m, 4H), 1.80 (m, 4H), 1.30 (m, 80H), 0.88 (t,
15H).
2-(2-Aminoethyl)-4-dioctylamino-6-{(3,4,5-tridodecyloxyphe-
nyl)amino}-[1,3,5]triazine (1): A dry THF solution of compound
4 (450 mg) and 10 equiv of 1,2-diaminoethane was refluxed
overnight under a nitrogen atmosphere. After cooling to room
temperature, the mixture was filtered to remove the resulting
precipitates. The filtrate was evaporated, and the residue was
redissolved in CHCl3. The resulting solution was washed with 2
M hydrochloric acid and then water, and the separated organic phase
was dried over Na2SO4. After the solvent was evaporated, the
residue was purified by silica gel column chromatography (10%
MeOH in CHCl3 as an eluent) to give compound 1 (338 mg, 73%
1
yield): H NMR (400 MHz, CDCl3) δ ) 6.86 (s, 2H), 3.86 (m,
6H), 3.77 (m, 2H), 3.51 (m, 2H), 3.40 (m, 2H), 3.30 (m, 2H), 1.72
(m, 6H), 1.53 (m, 4H), 1.38-1.22 (m, 74H), 0.88 (t, 15H).
2-(3-Aminopropyl)-4-dioctylamino-6-{(3,4,5-tridodecyloxyphe-
nyl)amino}-[1,3,5]triazine (2): This compound was prepared from
400 mg of 4 and 10 equiv of 1,3-diaminopropane in the same way
26.4, 25.6, 21.9, 13.4. MS (MALDI-TOF) calcd for C152H246
-
N14O10 (m/z) 2429.7 [M+], found 2430.0. Anal. Calcd for
C
152H246N14O10 ·3H2O: C, 73.50; H, 10.23; N, 7.90. Found: C,
73.21; H, 10.34; N, 7.86.
1
as described for 1 (yield 290 mg (70%)): H NMR (400 MHz,
CDCl3) δ ) 6.88 (s, 2H), 3.91 (m, 6H), 3.60 (m, 2H), 3.50 (m,
4H), 3.11 (m, 2H), 2.07 (m, 2H), 1.72 (m, 6H), 1.59 (m, 4H), 1.30
(m, 74H), 0.88 (t, 15H).
N,N′-Bis[2-{4-dioctylamino-6-(3,4,5-tris-dodecyloxy-phenyl)-
amino-[1,3,5]triazin-2-ylamino}-ethyl]perylene-3,4:9,10-tetracar-
boxylic Acid Bisimide (MPBI2): Perylene-3,4:9,10-tetracarboxylic
acid bisanhydride (44 mg, 0.11 mmol), compound 1 (338 mg, 0.330
mmol), zinc acetate (50 mg), and imidazole (3.1 g) were refluxed
under nitrogen overnight. After cooling to room temperature, the
mixture was dissolved in CHCl3 and washed with 2 M hydrochloric
Acknowledgment. We thank Ms. Kanako Unoike of Chiba
University for the measurement of AFM and Dr. Yasuo
Norikane and Dr. Nobuyuki Tamaoki of National Institute of
Advanced Industrial Science and Technology (AIST, Tsukuba,
Japan) for MALDI-TOF MS measurement.
Supporting Information Available: Materials and methods
1
and H and 13C NMR spectra of MPBI2 and MPBI3. This
material is available free of charge via the Internet at
(45) Percec, V.; Ahn, C.-H.; Bera, T. K.; Ungar, G.; Yeardley, D. J. P.
Chem.-Eur. J. 1999, 5, 1070–1083.
JO800338F
J. Org. Chem. Vol. 73, No. 9, 2008 3335