MS: m/z 599 [M+]. Anal. Calc. for C42H33NO3: C, 84.11; H, 5.55.
(E)-2-((E)-4-(Bis(7-hexyl-9,9-dimethyl-9H-fluoren-2-yl)-
amino)styryl)-4-((5-carboxy-3,3-dimethyl-1-octyl-3H-in-
dolium-2-yl)methylene)-3-oxocyclobut-1-enolate (JK-64Hx)
Found: C, 83.91; H, 5.34.
(E)-3-(4-(Bis(7-hexyl-9,9-dimethyl-9H-fluoren-2-yl)amino)styryl)-
4-hydroxycyclobut-3-ene-1,2-dione (4)
JK-64Hx was synthesized by a similar procedure to JK-64,
except that 4 (200 mg, 0.26 mmol) was used instead of 3. Yield:
85%. Mp: 193 ꢂC. 1H NMR (DMSO-d6): d 8.21 (s, 1H), 8.06 (d, J
¼ 7.2 Hz, 1H), 7.85 (d, J ¼ 16.0 Hz, 1H), 7.69 (d, J ¼ 8.5 Hz, 2H),
7.66 (d, J ¼ 7.7 Hz, 2H), 7.49 (d, J ¼ 7.8 Hz, 2H), 7.22 (d, J ¼ 8.5
Hz, 2H), 7.23 (s, 2H), 7.16 (d, J ¼ 7.8 Hz, 2H), 7.16 (s, 2H), 7.11
(d, J ¼ 7.7 Hz, 2H), 6.92 (d, J ¼ 16.0 Hz, 1H), 6.99 (d, J ¼ 7.2 Hz,
1H), 6.24 (s, 1H), 4.37 (m, 2H), 2.66 (t, J ¼ 8.1 Hz, 4H), 1.95 (m,
2H), 1.75 (s, 6H), 1.64 (m, 4H), 1.47 (m, 6H), 1.36 (s, 12H), 1.35–
1.30 (m, 4H), 1.28 (m, 12H), 0.88 (t, J ¼ 6.9 Hz, 3H), 0.87 (t, J ¼
6.9 Hz, 6H). 13C{1H} NMR (DMSO-d6): d 191.0, 183.0, 176.9,
177.5, 172.3, 169.7, 166.8, 154.6, 153.5, 149.1, 145.2, 144.6, 142.9,
141.4, 137.6, 135.7, 135.2, 130.2, 129.7, 129.2, 128.6, 127.2, 124.2,
123.6, 122.6, 120.9, 119.6, 118.5, 112.9, 60.2, 46.5, 44.8, 35.5,
33.7, 31.8, 31.4, 31.1, 29.2, 28.5, 27.3, 26.7, 26.0, 22.7, 22.0, 20.8,
14.2, 13.9. MS: m/z 1064 [M+]. Anal. Calc. for C74H84N2O4: C,
83.42; H, 7.95. Found: C, 82.91; H, 7.52.
4 was synthesized by a similar procedure to 3, except that 2 (0.2 g,
0.246 mmol) was used instead of 1. Yield: 90%. Mp: 193 ꢂC. 1H
NMR (CDCl3): d 7.88 (d, J ¼ 16.2 Hz, 1H), 7.59 (d, J ¼ 8.7 Hz,
2H), 7.56 (d, J ¼ 7.5 Hz, 2H), 7.47 (d, J ¼ 7.8 Hz, 2H), 7.22 (d, J
¼ 8.7 Hz, 2H), 7.20 (s, 2H), 7.14 (d, J ¼ 7.8 Hz, 2H), 7.12 (s, 2H),
7.11 (d, J ¼ 7.5 Hz, 2H), 6.92 (d, J ¼ 16.2 Hz, 1H), 2.66 (t, J ¼ 8.1
Hz, 4H), 1.64 (m, 4H), 1.43 (s, 12H), 1.40 (m, 4H), 1.25 (m, 8H),
0.88 (t, J ¼ 6.9 Hz, 6H). 13C{1H} NMR (CDCl3): d 193.1, 192.5,
191.4, 175.5, 155.1, 153.3, 150.2, 146.7, 142.3, 142.1, 137.3, 136.8,
129.3, 128.0, 127.4, 124.2, 122.4, 121.6, 120.5, 119.9, 119.3, 111.7,
46.8, 36.4, 31.8, 31.1, 29.2, 27.2, 22.7, 14.2. MS: m/z 767 [M+].
Anal. Calc. for C54H57NO3: C, 84.45; H, 7.48. Found: C, 84.13;
H, 7.25.
(E)-3-(4-(Bis(4-(hexyloxy)phenyl)amino)styryl)-4-hydroxy-
cyclobut-3-ene-1,2-dione (6)
(E)-2-((E)-4-(Bis(4-(hexyloxy)phenyl)amino)styryl)-4-((5-carboxy-
-3,3-dimethyl-1-octyl-3H-indolium-2-yl)methyl-ene)-3-oxocy-
clobut-1-enolate (JK-65)
6 was synthesized by a similar procedure to 3, except that 5ꢂ(0.2 g,
1
0.33 mmol) was used instead of 1. Yield: 90%. Mp: 191 C. H
NMR (CDCl3): 7.57 (d, 1H, J ¼ 16.2 Hz), 7.31 (d, 2H, J ¼ 8.4
Hz), 6.97 (d, 4H, J ¼ 8.7 Hz), 6.90 (d, 1H, J ¼ 16.2 Hz), 6.82 (d,
4H, J ¼ 9.0 Hz), 6.76 (d, 2H, J ¼ 8.07 Hz), 3.90 (t, 4H, J ¼ 6.6
Hz), 1.74 (m, 4H), 1.46 (m, 4H), 1.34 (m, 8H), 0.92 (t, 6H, J ¼ 6.9
Hz). 13C NMR (CD3OD): 209.4, 200.5, 179.4, 157.5, 151.1, 141.3,
136.8, 129.7, 129.4, 128.2, 120.4, 116.5, 112.9, 69.3, 32.8, 30.4,
26.9, 23.7, 14.4. Anal. Calc. for C36H41NO5: C, 76.16; H, 7.28.
Found: C, 76.20; H, 7.26.
JK-65 was synthesized by a similar procedure to JK-64, except
that 6 (110 mg, 0.19 mmol) was used instead of 3. Yield: 85%.
Mp: 189 ꢂC. 1H NMR (CDCl3): 8.20 (d, 1H, J ¼ 8.1 Hz), 8.17 (s,
1H), 8.08 (d, 1H, J ¼ 15.6 Hz), 7.43 (d, 2H, J ¼ 8.4 Hz), 7.20 (d,
1H, J ¼ 8.4 Hz), 7.07 (m, 5H), 6.86 (d, 4H, J ¼ 8.1 Hz), 6.82 (d,
2H, J ¼ 8.4 Hz), 6.3 (s, 1H), 4.21 (t, 2H, J ¼ 6.0 Hz), 3.94 (t, 4H, J
¼ 6.3 Hz), 1.85 (s, 6H), 1.75 (m, 6H), 1.46 ꢀ 1.23 (m, 22H), 0.88
(m, 9H). 13C NMR (CDCl3): 189.7, 185.5, 181.3, 178.1, 176.4,
169.4, 156.8, 151.5, 145.6, 143.2, 139.1, 130.6, 130.3, 128.4, 128.1,
127.8, 127.6, 118.7, 118.2, 115.9, 115.6, 115.4, 68.4, 50.8, 31.7,
29.4, 29.2, 27.7, 27.0, 26.7, 26.4, 26.2, 25.9, 22.8, 22.7, 14.3, 14.2,
14.1. Anal. Calc. for C56H68N2O6: C, 77.74; H, 7.92. Found: C,
77.68; H, 7.90.
(E)-2-((E)-4-(Bis(9,9-dimethyl-9H-fluoren-2-yl)amino)styryl)-4-
((5-carboxy-3,3-dimethyl-1-octyl-3H-indolium-2-yl) methy-
lene)-3-oxocyclobut-1-enolate (JK-64)
0.19 g (0.317 mmol) of 3 and 0.14 g (0.317 mmol) of 5-carboxy-
2,3,3-trimethyl-1-octyl-3H-indolium were dissolved in a mixture
of 50 ml benzene and 50 ml n-butanol. The mixture was refluxed
with a Dean–Stark apparatus for 18 h. The solvent was partly
removed until the product precipitated. The pure product JK-64
was obtained by silica gel chromatography (eluent Mc : MeOH
Acknowledgements
This work was supported by the Korea Science and Engineering
Foundation (KOSEF) through the National Research Lab.
Program funded by the Ministry of Science and Technology (No.
R0A-2005-000-10034-0) and WCU (the Ministry of Education
and Science) Program (No. R31-2008-000-10035-0) and the
MKE (The Ministry of Knowledge and Economy) under the
ITRC (Information Technology Research Center) program
(IITA-2008-C1090-0804-0013).
ꢂ
1
¼ 10 : 1, Rf 0.4) to afford JK-64 in 81% yield. Mp: 197 C. H
NMR (DMSO-d6): d 8.21 (s, 1H), 8.06 (d, J ¼ 7.2 Hz, 1H), 7.78
(t, J ¼ 7.8 Hz, 2H), 7.76 (d, J ¼ 8.7 Hz, 2H), 7.65 (m, 1H), 7.61 (d,
J ¼ 7.6 Hz, 2H), 7.49 (d, J ¼ 8.7 Hz, 2H), 7.33 (s, 2H), 7.30 (t, J ¼
7.8 Hz, 2H), 7.29 (d, J ¼ 7.8 Hz, 2H), 7.28 (m, 1H), 7.11 (d, J ¼
7.6 Hz, 2H), 7.02 (d, J ¼ 7.2 Hz, 1H), 6.99 (d, J ¼ 7.8 Hz, 2H),
6.24 (s, 1H), 4.37 (m, 2H), 1.95 (m, 2H), 1.75 (s, 6H), 1.47 (m,
2H), 1.36 (s, 12H), 1.35–1.30 (m, 4H), 1.28 (m, 4H), 0.88 (t, J ¼
6.9 Hz, 3H). 13C{1H} NMR (DMSO-d6): d 184.7, 184.3, 179.1,
176.5, 175.0, 172.3, 169.9, 167.0, 155.4, 155.0, 153.3, 150.7, 146.1,
145.7, 143.5, 138.7, 138.1, 135.7, 135.0, 131.6, 129.9, 128.7, 127.1,
125.0, 124.4, 122.7, 121.7, 120.9, 120.5, 110.5, 54.9, 46.5, 44.8,
33.7, 31.1, 28.5, 27.3, 26.7, 26.0, 22.0, 20.8, 13.9. MS: m/z 896
[M+]. Anal. Calc. for C62H60N2O4: C, 83.00; H, 6.74. Found: C,
82.81; H, 6.54.
Notes and references
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T. Kitamura, Y. Wada and S. Yanagida, Electrochem. Commun.,
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€
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This journal is ª The Royal Society of Chemistry 2010
J. Mater. Chem., 2010, 20, 3280–3286 | 3285