616
M. Matsui et al. / Dyes and Pigments 96 (2013) 614e618
Table 1
Properties of GU104.
a
a
b
c
Compd
lmax
(
3 )
nm
Fmax
nm
Eox
V
Eox ꢀ E0-0
ꢀ1.67
V
HOMOd
eV
LUMOd
eV
fe
GU104
392 (15,100), 541 (34,600)
642
þ0.44
ꢀ5.35
ꢀ2.60
1.02
Measured on 1.0 ꢂ 10ꢀ5 mol dmꢀ3 of substrate in chloroform at 25 ꢁC.
a
b
c
vs Fc/Fcþ in DMF.
Calculated on the basis of Eox and lint
Calculated by the B3LYP/6-31G(d,p)//B3LYP/3-21G level.
Oscillator strength calculated by the INDO/S method.
.
d
e
3. Conclusion
2-dicyclohexylphosphyno-20,60-dimethoxybiphenyl (SPhos,1.000 g,
2.44 mmol). The mixture was refluxed overnight. After the reaction
was completed, the mixture was poured into water (300 mL). The
product was extracted with chloroform (100 mL ꢂ 3). The extract
was washed with water (100 mL ꢂ 3) and dried over anhydrous
sodium sulfate. The product was purified by column chromatog-
raphy (SiO2, CHCl3:C6H14 ¼1:1) to give pale yellow liquid. Yield 31%;
We have made a molecular design, synthesis, and evaluation of
a new indoline dye GU104 in which dicyanovinylidene rhodanine
moiety is attached to the indoline moiety through an p-phenylene
spacer on the indolineenitrogen atom. GU104 could have more
positive Eox level than D149. Cell performance in the presence of
CA, CDCA, or LDA was greatest for LCA as this showed the greatest
reduction in dye H-aggregate formation.
1H NMR (CDCl3)
d
¼ 0.85e0.99 (m,1H),1.24e1.32 (m,1H),1.38e1.52
(m, 1H), 1.63e1.75 (m, 1H), 1.89e2.12 (m, 2H), 3.87e3.94 (m, 1H),
4.58e4.74 (m, 1H), 6.89 (t, J ¼ 7.8 Hz, 1H), 7.14 (t, J ¼ 7.8 Hz, 1H), 7.18
(d, J ¼ 7.8 Hz,1H), 7.27 (d, J ¼ 7.8 Hz,1H), 7.34 (d, J ¼ 8.7 Hz, 2H), 7.81
4. Experimental
(d, J ¼ 8.7 Hz, 2H), 9.82 (s, 1H); 13C NMR (CDCl3)
¼ 24.7, 34.1 (2C),
d
45.5, 68.5,110.7,115.9 (2C),121.2,125.0,127.1,128.3,131.5 (2C),136.0,
144.7, 148.7, 190.3; IR (KBr) 2928, 2855, 1744, 1686, 1589, 1481,
1381 cmꢀ1; EIMS (70 eV) m/z (rel intensity) 263 (Mþ, 52), 234 (100),
104 (14); Anal. Found: 82.43; H, 6.90; N, 5.71%. Calcd for C18H17NO:
C, 82.10, H, 6.51; N, 5.32%.
4.1. Instruments
Melting points were measured with a Yanaco MP-S2 micro-
melting-point apparatus. NMR spectra were taken with a JEOL
JNM-ECX 400P spectrometer. Mass spectra were taken on a JEOL
MStation 700 spectrometer. Elemental analysis was performed
with a Yanaco MT-6 CHN corder. UVevis absorption and fluores-
cence spectra were taken on Hitachi U-3500 and F-4500 spec-
trophotometers, respectively. Electrochemical measurement was
carried out using an EG&G Princeton Applied Research Potentio-
stat/Galvanostat (Model 263A) driven by the M270 software
package.
4.4. Synthesis of GU104
To 1-butanol (10 mL) were added 3 (200 mg, 0.76 mmol),
a dicyanovinylidene double rhodanine acetic acid 4 (341 mg,
0.76 mmol). The mixture was heated to 120 ꢁC. Then, to the mixture
was added piperidine (65 mg, 0.76 mmol). The mixture was
refluxed for 4 h. After the reaction was completed, the solvent was
removed in vacuo. The product was purified by column chroma-
tography (SiO2, CHCl3:MeOH ¼ 20:1). The 13C NMR spectrum was
not measured due to low solubility. Yield 69%; mp 242e243 ꢁC; 1H
4.2. Materials
Compounds 1 and 4 were supplied from Chemicrea Co., Ltd.
NMR (DMSO-d6)
d
¼ 0.85 (t, J ¼ 6.6 Hz, 3H), 1.17e1.36 (m, 11H),
4.3. Synthesis of 10-(4-formylphenyl)-6b,7,8,9,9a,10-hexahydro[g]
cyclopenta[b]indole (3)
1.55e1.68 (m, 3H), 1.71e1.87 (m, 2H), 1.98e2.11 (m, 2H), 3.85e3.93
(m, 1H), 3.97 (s, 2H), 4.54 (s, 2H), 4.75e4.83 (m, 1H), 6.88 (t,
J ¼ 7.7 Hz, 1H), 7.13 (t, J ¼ 7.7 Hz, 1H), 7.23 (d, J ¼ 7.7 Hz, 1H), 7.32 (d,
J ¼ 7.7 Hz,1H), 7.46 (d, J ¼ 8.5 Hz, 2H), 7.67 (d, J ¼ 8.5 Hz, 2H), 7.76 (s,
1H); IR (KBr) 2928, 2195,1655,1578,1543,1508 cmꢀ1; FABMS (NBA)
m/z 680 (MHþ); Anal. Found: C, 65.07; H, 5.63; N, 10.39%. Calcd for
C37H37N5O4S2: C, 65.37; H, 5.49; N, 10.30%.
To toluene (300 mL) were added 1,2,3,3a,4,8b-hexahy-
drocyclopenta[b]indole (1, 3.986 g, 25.0 mmol), 4-bromobenzal-
dehyde (2, 6.547 g, 30.0 mmol), sodium t-butoxide (3.360 g,
35.0 mmol), palladium diacetate (0.281 g, 1.25 mmol), and
Fig. 2. DFT calculations (B3LYP/6-31G(d,p)//B3LYP/3-21G) of GU104. (a) optimized structure, (b) HOMO and LUMO levels, and (c) isodensity surface plots.