176
6 Thermo-Responsive Phosphorescence Control Mediated …
Synthesis of 1-d 4
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
D
D
D
D
D
D
D
D
1-d 4
1-d 4 was prepared from 1,4-diethynyl-C 6 D 4 [18] (0.065 g, 0.50 mmol) according
to the procedure similar to that described for the preparation of 1. Yield: 82% (0.473 g,
0.41 mmol, green solid).
1 H NMR (400 MHz, CDCl 3 , δ): 7.18 (dt, J = 4.3 Hz, 12.1 Hz,
12H), 7.50–7.56 (m, 12H).
13 C NMR (100 MHz, CDCl 3 , δ): 104.5, 116.8–117.2 (m),
123.0, 125.3 (d, J = 57.8 Hz), 131.7 (t, J = 25.2 Hz), 136.3–136.6 (m), 165.0 (d, J =
259.1 Hz). MS-ESI (m/z): calculated for C 46 H 24 D 4 Au 2 F 6 P 2 , 1155.11861 (49.8%);
found, 1155.12308. Anal. Calcd for C 46 H 24 D 4 Au 2 F 6 P 2 : C, 47.85; H, 2.79; Found:
C, 47.83; H, 2.37.
Synthesis of 2
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
2

2 was prepared from 1,4-diethynyl-tetramethylbenzene [19] (0.091 g, 0.50 mmol)
according to the procedure similar to that described for the preparation of 1. Yield:
71% (0.428 g, 0.36 mmol, yellow solid).
1 H NMR (400 MHz, CDCl 3 , δ): 2.52 (s,
12H), 7.19 (dt, J = 4.4 Hz, 12.1 Hz, 12H), 7.51–7.58 (m, 12H).
13 C NMR (100 MHz,
CDCl 3 , δ): 19.2, 103.0, 116.7–117.1 (m), 123.6, 125.6 (d, J = 55.3 Hz), 135.6, 136.4–
136.7 (m), 165.0 (d, J = 258.5 Hz). MS-ESI (m/z): calculated for C 50 H 36 Au 2 F 6 P 2 ,
1207.15610 (54.1%); found, 1207.16057 Anal. Calcd for C 50 H 36 Au 2 F 6 P 2 : C, 49.77;
H, 3.01; Found: C, 49.33; H, 2.97.
6.9.3 TGA of 1 and 2
See Fig. 6.11.
6.9.4 Data for Single-Crystal X-ray Structural Analyses
Single-crystal X-ray structural analyses were carried out on a Rigaku R-AXIS RAPID
diffractometer using graphite monochromated Mo-K α radiation. The structure was