Y. Lin et al. / Dyes and Pigments 99 (2013) 995e1003
997
13C NMR (100 MHz, CDCl3):
d
15.6 (CH3), 95.3, 104.4, 123.0, 125.2,
(400 MHz, CDCl3):
d
2.04 (s, 3H, CH3), 2.17 (s, 3H, CH3), 3.49 (s, 1H, e
131.7, 141.5. Anal. Calcd for C25H26F6S2Si2: C, 53.55; H, 4.67. Found:
C, 53.70; H, 4.66.
C^CH), 3.50 (s, 1H, eC^CH), 7.15 (s, 1H, thiophene-H), 7.29e7.50
(m, 5H, ph-H). 13C NMR (100 MHz, CDCl3):
d
14.9, 15.3 (CH3), 74.8,
76.8, 86.1, 92.5, 117.2, 118.7, 121.5, 122.5, 124.8, 125.0, 128.7, 129.1,
129.8, 129.9, 130.5, 131.8, 132.8, 134.8, 142.8. Anal. Calcd for
2.2.4. Synthesis of 1-[2-methyl-5-phenyl-3-thienyl]
heptafluorocyclopentene (6)
C25H14F6S2: C, 60.97; H, 2.87. Found: C, 60.77; H, 2.56.
n-Butyllithium (1.6 mL, 4.0 mmol, 2.5 M in hexane)was added to
a solution of bromothiophene derivative 5 (0.5 g, 1.98 mmol) in THF
(40 mL) at ꢀ78 ꢁC under argon atmosphere. After the mixture was
stirred for 30 min, perfluorocyclopentene (0.38 g, 1.8 mmol) was
added in one portion. The solution was allowed to warm to 10 ꢁC
with stirring. Water was added to the reaction mixture. The reac-
tion mixture was extracted with ether, washed with water, dried
over sodium sulfate, and concentrated. Column chromatography
(silica, hexane) gave compound 6 (0.3 g) as a colorless wax. Yield:
2.2.8. General synthesis of compounds LAu-C^C-DTE-C^C-AuL (II)
The terminal diacetylene I (0.11 mmol) was dissolved in an
anhydrous methanol (10 mL) under nitrogen. This solution was
added to the dry THF solution (10 mL) of AuCl(PPh3) (0.20 mmol)
and the mixture was stirred at room temperature. The methanol
solution (5 mL) of NaOH (200 mg, 0.5 mmol) was added dropwise
to the mixture. After 2 h, a pale-yellow precipitate appeared in the
solution. The precipitate was collected by filtration with a suction
filter and washed with MeOH, H2O, and ether successively. The
powder was dried under vacuum for 2 h.
42%. 1H NMR (CDCl3, 400 MHz)
d: 2.39 (s, 3 H, CH3), 7.02 (s, 1 H,
thiophene-H), 7.24e7.50 (m, 5H, ph-H). Anal. Calcd for C16H9F7S: C,
52.46; H, 2.48. Found: C, 52.51; H, 2.52.
[(PCy3Au)2{
IR, nmax cmꢀ1: 2112 (AueC^C). 1H NMR (400 MHz, CDCl3):
2.0 (m, 66H, Cy, CH3), 2.39 (s, 6H, CH3), 6.80 (s, 2H, thiophene-H).
31P NMR (160 MHz, CDCl3): 54.4 (s). 13C NMR (100 MHz, CDCl3):
15.6 (CH3), 25.9, 27.1, 30.7, 33.1, 94.5, 125.2, 125.7, 130.6, 137.0,
m
-Bis(2-ethynyl)-DTE}] (II-2a): Yield: 0.11 g, 80%.
d
1.26e
2.2.5. Synthesis of 1-[2-methyl-5-phenyl-3-thienyl]-2-[4-methyl-
2,5-bis(tri-methylsilylethynyl)-3-thienyl]hexafluorocyclopentene
(8)
d
d
n-Butyllithium (1.6 mL, 4.0 mmol, 2.5 M in hexane) was added
to a solution of 3-bromo-4-methyl-2,5-bis(trimethylsilylethynyl)
thiophene 7 (0.31 g, 1.2 mmol) in THF (15 mL) at ꢀ78 ꢁC under
argon atmosphere. After the mixture was stirred for 30 min, a so-
148.8, 150.1. Anal. Calcd for C55H74Au2F6P2S2: C, 48.25; H, 5.45.
Found: C, 48.47; H, 5.61.
[(PPh3Au)2{
IR, nmax cmꢀ1: 2099 (AueC^C). 1H NMR (400 MHz, CDCl3):
6H, CH3), 6.81 (s, 2H, thiophene-H), 7.46e7.56 (m, 30H, Ph). 31P
NMR (160 MHz, CDCl3): 15.3
40.3 (s). 13C NMR (100 MHz, CDCl3):
m-Bis(2-ethynyl)-DTE}] (II-2b): Yield: 0.095 g, 71%.
d
2.00 (s,
lution of monosubstituted perfluorocyclopentene
6 (0.48 g,
1.0 mmol) in THF (10 mL) was added dropwise. The solution was
allowed to warm to 10 ꢁC with stirring. Water was added to the
reaction mixture. The reaction mixture was extracted with ether,
washed with water, dried over magnesium sulfate, and concen-
trated. Column chromatography (silica, hexane) gave compound 8
(0.23 g) as a yellow wax. Yield: 37%. IR, nmax cmꢀ1: 2148(C^C). 1H
d
d
(CH3), 94.0, 125.1, 129.1, 129.5, 130.0, 131.1, 131.6, 134.3, 138.1. Anal.
Calcd for C55H38Au2F6P2S2: C, 49.56; H, 2.87. Found: C, 49.83; H,
2.99.
[(PPh3Au)2{
IR, nmax cmꢀ1: 2092 (AueC^C). 1H NMR (400 MHz, CDCl3):
6H, CH3), 2.17 (s, 6H, CH3), 7.11 (s, 1H, thiophene-H), 7.43e7.54 (m,
30H, Ph). 31P NMR (160 MHz, CDCl3): 39.8 (s). 13C NMR (100 MHz,
CDCl3): 14.6 (CH3),14.8, 95.3,120.8,123.9,125.5,127.2,128.7,129.1,
m-2,5-bis(ethynyl)-DTE }] (II-3): Yield: 0.12 g, 85%.
d
2.10 (s,
NMR (400 MHz, CDCl3):
CH3), 2.19 (s, 3H, CH3), 7.18 (s, 1H, thiophene-H), 7.27e7.49 (m, 5H,
ph-H). 13C NMR (100 MHz, CDCl3):
14.5, 15.6, 89.2, 94.3, 102.2,
d 0.19e0.24 (m, 18H, SiMe3), 1.99 (s, 3H,
d
d
d
104.4, 114.6, 121.5, 122.8, 123.0, 123.3, 124.2, 124. 8, 125.2, 126.0,
126.1, 126.5, 128.6, 128.9, 129.5, 130.5, 132.7, 138.8. Anal. Calcd for
129.4, 130.0, 130.2, 131.6, 134.0, 134.8, 139.1, 140.8, 141.6. Anal. Calcd
for C61H42Au2F6P2S2: C, 52.00; H, 3.00. Found: C, 52.29; H, 2.73.
C
31H30F6S2Si2: C, 58.46; H, 4.75. Found: C, 58.61; H, 4.48.
2.3. Crystallographic details for (I-2)
2.2.6. Synthesis of 1,2-bis(2-ethynyl-5-methyl-3-thienyl)
perfluorocyclopentene (I-2)
Crystals suitable for X-ray diffraction were grown from a
dichloromethane of solution I-2 layered with hexane. A crystal with
approximate dimensions of 0.40 ꢂ 0.20 ꢂ 0.10 mm3 was mounted
on a glass fiber for diffraction experiment. Intensity data were
To a flask containing 4 (0.42 g, 0.85 mmol) was added a solution
of NaOH (0.44 mg, 11.0 mmol) in methanol/THF (50 mL/15 mL), and
the resulting mixture was stirred at room temperature for 30 min.
The reaction was diluted with dichloromethane, washed with wa-
ter, and extracted with dichloromethane. The combined dichloro-
methane phases were then dried (Na2SO4) and evaporated.
Chromatography over silica gel (hexane) afforded I-2 (0.29 g) as a
yellow solid. Yield: 82%. IR, nmax cmꢀ1: 3320 (^CeH); 2162(C^C).
collected on a Nonius Kappa CCD diffractometer with Mo Ka radi-
ꢀ
ation (0.71073 A) at 293 K. The structure was solved by a combi-
nation of direct methods (SHELXS-97) and Fourier difference
techniques and refined by full-matrix least squares (SHELXL-97).
All non-H atoms were refined anisotropically. The hydrogen atoms
were placed in the ideal positions and refined as riding atoms.
Further crystal data and details of the data collection are summa-
rized in Table 1.
1H NMR (400 MHz, CDCl3):
6.78 (s, 2 H, thiophene-H). 13C NMR (100 MHz, CDCl3):
74.8, 86.1, 121.5, 124.8, 132.8, 142.3. Anal. Calcd for C19H10F6S2: C,
54.80; H, 2.42. Found: C, 54.67; H, 2.46.
d
2.45 (s, 6 H, CH3), 3.23 (s, 3 H, C^CH),
15.3 (CH3),
d
2.4. Photochemical measurements
2.2.7. Synthesis of 1-[2-methyl-5-phenyl-3-thienyl]-2-[4-methyl-
2,5-bis(ethynyl)-3-thienyl]hexafluorocyclopentene (I-3)
Absorption spectra were measured on U-3310 UV spectropho-
tometer using quartz cuvettes of 1 cm path length. UV light was
irradiated using ZF5 UV lamp (302 nm), and visible light irradiation
To a flask containing 8 (0.64 g,1.0 mmol) was added a solution of
NaOH (0.80 g, 2.0 mmol) in methanol/THF (50 mL/15 mL), and the
resulting mixture was stirred at room temperature for 30 min. The
reaction was diluted with dichloromethane, washed with water,
and extracted with dichloromethane. The combined dichloro-
methane phases were then dried (Na2SO4) and evaporated. Chro-
matography over silica gel (hexane) afforded I-3 (0.38 g) as a yellow
solid. Yield: 78%. IR, nmax cmꢀ1: 3326 (^CeH); 2158(C^C). 1H NMR
(l
> 420 nm) was carried out by using a LZG 220 V 500 W tungsten
lamp with cutoff filters. The irradiating light (
l
¼ 550 nm) was
obtained by passing the light through a band-pass filter. Quantum
yields for cyclization and cycloreversion reactions were determined
by comparing the reaction yields of the diarylethenes against 1,2-
bis (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene. The