6.9 Experimental Section
175
Fluorescence microscopic spectra were recorded on a Photonic Hamamatsu PMA12 Multichannel Analyzer. The emission quantum yields of the solid samples at
room temperature were recorded on a Hamamatsu Quantaurus-QY spectrometer
with an integrating sphere. Variable temperature emission decay measurements were
obtained using an FLS 920 spectrometer from Edinburgh Instruments equipped with
a micro halogen lamp (μF). Elemental analyses and low- and high-resolution mass
spectra were recorded at the Global Facility Center at Hokkaido University. Photographs were obtained using Olympus BX51 or SZX7 microscopes with Olympus
DP72, Nikon D5100 digital cameras. Thermal gravimetric analysis profiles were
recorded on Bruker TG-DTA2010SAT. Differential Scanning Calorimetry (DSC)
profiles were measured on Perkin Elmer DSC8000 with an Intracooler II. The raw
data files were plotted on Igor Pro Version 6.37.
6.9.2 Synthesis
Synthesis of 1
THF (2 ml)
78°C, 2h
n-BuLi (2.0 equiv.)
Cl Au P
F
3
(2.0 equiv.)
0°C, 2h
0.5 mmol
P
P
Au
Au
F
F
F
F
F
F
1
A powder of 1,4-diethynylbenzene (0.063 g, 0.50 mmol) was placed in an ovendried two neck flask. The flask was connected to vacuum/nitrogen manifold through
a rubber tube. It was evacuated and then backfilled with nitrogen. This process was
repeated three times. Dry THF (3.0 ml) was then added to the flask under nitrogen
atmosphere. After cooling to −78 °C, n-BuLi in Hexane (0.61 ml, 1.00 mmol, 1.63 M)
was added to the mixture dropwise and stirred for 2 h. The suspended THF solution
was added tris(4-fluorophenyl)phosphane gold(I) complex [8] (0.549 g, 1.00 mmol),
and the reaction was performed under 0 °C for 2 h. The reaction was quenched by
addition of a phosphate buffer solution and then extracted with CHCl 3 three times and
washed with H 2 O and brine. The organic layers were collected and dried over MgSO 4 .
After filtration, the solvent was removed in vacuo. Further purification by filtration
washed with Et 2 O and recrystallization using CHCl 3 /Hexane gave analytically pure
green crystals of 1 with green emission under UV light. (0.449 g, 0.39 mmol, 78%).
1 H NMR (400 MHz, CDCl 3 , δ): 7.18 (dt, J = 4.4 Hz, 12.1 Hz, 12H), 7.38 (s, 4H),
7.50–7.56 (m, 12H).
13 C NMR (100 MHz, CDCl 3 , δ): 104.6, 116.8–117.2 (m), 123.2,
125.3 (d, J = 58.2 Hz), 132.1, 136.4–136.6 (m), 165.0 (d, J = 256.0 Hz). MS-ESI
(m/z): calculated for C 46 H 28 Au 2 F 6 P 2 , 1151.09350; found, 1151.09797. Anal. Calcd
for C 46 H 28 Au 2 F 6 P 2 : C, 48.02; H, 2.45; Found: C, 48.83; H, 2.33.
175
Fluorescence microscopic spectra were recorded on a Photonic Hamamatsu PMA12 Multichannel Analyzer. The emission quantum yields of the solid samples at
room temperature were recorded on a Hamamatsu Quantaurus-QY spectrometer
with an integrating sphere. Variable temperature emission decay measurements were
obtained using an FLS 920 spectrometer from Edinburgh Instruments equipped with
a micro halogen lamp (μF). Elemental analyses and low- and high-resolution mass
spectra were recorded at the Global Facility Center at Hokkaido University. Photographs were obtained using Olympus BX51 or SZX7 microscopes with Olympus
DP72, Nikon D5100 digital cameras. Thermal gravimetric analysis profiles were
recorded on Bruker TG-DTA2010SAT. Differential Scanning Calorimetry (DSC)
profiles were measured on Perkin Elmer DSC8000 with an Intracooler II. The raw
data files were plotted on Igor Pro Version 6.37.
6.9.2 Synthesis
Synthesis of 1
THF (2 ml)
78°C, 2h
n-BuLi (2.0 equiv.)
Cl Au P
F
3
(2.0 equiv.)
0°C, 2h
0.5 mmol
P
P
Au
Au
F
F
F
F
F
F
1
A powder of 1,4-diethynylbenzene (0.063 g, 0.50 mmol) was placed in an ovendried two neck flask. The flask was connected to vacuum/nitrogen manifold through
a rubber tube. It was evacuated and then backfilled with nitrogen. This process was
repeated three times. Dry THF (3.0 ml) was then added to the flask under nitrogen
atmosphere. After cooling to −78 °C, n-BuLi in Hexane (0.61 ml, 1.00 mmol, 1.63 M)
was added to the mixture dropwise and stirred for 2 h. The suspended THF solution
was added tris(4-fluorophenyl)phosphane gold(I) complex [8] (0.549 g, 1.00 mmol),
and the reaction was performed under 0 °C for 2 h. The reaction was quenched by
addition of a phosphate buffer solution and then extracted with CHCl 3 three times and
washed with H 2 O and brine. The organic layers were collected and dried over MgSO 4 .
After filtration, the solvent was removed in vacuo. Further purification by filtration
washed with Et 2 O and recrystallization using CHCl 3 /Hexane gave analytically pure
green crystals of 1 with green emission under UV light. (0.449 g, 0.39 mmol, 78%).
1 H NMR (400 MHz, CDCl 3 , δ): 7.18 (dt, J = 4.4 Hz, 12.1 Hz, 12H), 7.38 (s, 4H),
7.50–7.56 (m, 12H).
13 C NMR (100 MHz, CDCl 3 , δ): 104.6, 116.8–117.2 (m), 123.2,
125.3 (d, J = 58.2 Hz), 132.1, 136.4–136.6 (m), 165.0 (d, J = 256.0 Hz). MS-ESI
(m/z): calculated for C 46 H 28 Au 2 F 6 P 2 , 1151.09350; found, 1151.09797. Anal. Calcd
for C 46 H 28 Au 2 F 6 P 2 : C, 48.02; H, 2.45; Found: C, 48.83; H, 2.33.