3.2 Synthesis and Preparation
85
by a mortar and pestle or ball mill at room temperature, a powder of (rac)-1G ground
exhibiting red emission was formed. Similar mechanical stimulation of the greenemitting crystals of (S)-1G gave the powder (S)-1G ground , which has a similar
emission color to that of (rac)-1G crystals.
3.2.1 Synthesis of (rac)-1 and (S)-1
Synthesis of (rac)-1.
THF, 0 °C, 1 h
ZnBr 2
0 °C, 4 h
MgBr / THF
(rac)-2
N
N
C
C
Au
Au
Cl
Cl
N
N
C
C
Au
Au
(rac)-1
A powder of zinc bromide (0.067 g, 0.30 mol) was placed in an oven-dried twoneck flask. The flask was connected to a vacuum/nitrogen manifold through a rubber
tube. It was evacuated and then backfilled with nitrogen. This cycle was repeated three
times. THF (1.0 mL) was then added in the flask through the rubber septum using a
syringe and stirred at 0 °C. A phenylmagnesium bromide reagent in THF (0.400 ml,
0.30 mmol, 0.75 M) was then added to the reaction mixture using a syringe and
stirred at 0 °C for 1 h. Then, a solid of (rac)-2
10 (0.072 g, 0.10 mmol) was added and
the mixture was stirred at 0 °C. After the reaction completion was monitored by TLC
analysis, the reaction mixture was quenched by the addition of a phosphate buffer
solution and then extracted with CH 2 Cl 2 three times and washed with H2O and brine.
The organic layers were collected and dried over MgSO4. After filtration, the solvent
was removed in vacuo. Further purification by flash column chromatography (SiO 2 ,
CH 2 Cl 2 /hexane = 1:1) gave an analytically pure orange solid of (rac)-1 (0.060 g,
0.070 mmol, 70%).
1 H NMR (400 MHz, CDCl3, δ): 7.01–7.06 (m, 2H), 7.16–7.20
(m, 6H), 7.29 (dd, J = 1.6, 8.0 Hz, 4H), 7.52 (t, J = 7.8 Hz, 2H), 7.71–7.75 (m, 4H)
8.09 (d, J = 8.4 Hz, 2H), 8.20 (d, J = 8.2 Hz, 2H). 13C NMR (100 MHz, CDCl3,
δ): 122.7 (C), 123.2 (CH), 126.0 (CH), 126.2 (CH), 127.5 (CH), 129.2 (CH), 129.3
(CH), 131.0 (C), 131.6 (C), 132.1 (CH), 133.8 (C), 140.6 (CH), 162.5 (C), 164.6
(CH). MS-ESI (m/z): [M + Na] + calculated for C 34 H 22 Au 2 N 2 Na+, 875.10; found,
875.10. Anal. Calcd for C 34 H 22 Au 2 N 2 : C, 47.90; H, 2.60; N, 3.29. Found: C, 48.48;
H, 2.74; N, 3.10.
85
by a mortar and pestle or ball mill at room temperature, a powder of (rac)-1G ground
exhibiting red emission was formed. Similar mechanical stimulation of the greenemitting crystals of (S)-1G gave the powder (S)-1G ground , which has a similar
emission color to that of (rac)-1G crystals.
3.2.1 Synthesis of (rac)-1 and (S)-1
Synthesis of (rac)-1.
THF, 0 °C, 1 h
ZnBr 2
0 °C, 4 h
MgBr / THF
(rac)-2
N
N
C
C
Au
Au
Cl
Cl
N
N
C
C
Au
Au
(rac)-1
A powder of zinc bromide (0.067 g, 0.30 mol) was placed in an oven-dried twoneck flask. The flask was connected to a vacuum/nitrogen manifold through a rubber
tube. It was evacuated and then backfilled with nitrogen. This cycle was repeated three
times. THF (1.0 mL) was then added in the flask through the rubber septum using a
syringe and stirred at 0 °C. A phenylmagnesium bromide reagent in THF (0.400 ml,
0.30 mmol, 0.75 M) was then added to the reaction mixture using a syringe and
stirred at 0 °C for 1 h. Then, a solid of (rac)-2
10 (0.072 g, 0.10 mmol) was added and
the mixture was stirred at 0 °C. After the reaction completion was monitored by TLC
analysis, the reaction mixture was quenched by the addition of a phosphate buffer
solution and then extracted with CH 2 Cl 2 three times and washed with H2O and brine.
The organic layers were collected and dried over MgSO4. After filtration, the solvent
was removed in vacuo. Further purification by flash column chromatography (SiO 2 ,
CH 2 Cl 2 /hexane = 1:1) gave an analytically pure orange solid of (rac)-1 (0.060 g,
0.070 mmol, 70%).
1 H NMR (400 MHz, CDCl3, δ): 7.01–7.06 (m, 2H), 7.16–7.20
(m, 6H), 7.29 (dd, J = 1.6, 8.0 Hz, 4H), 7.52 (t, J = 7.8 Hz, 2H), 7.71–7.75 (m, 4H)
8.09 (d, J = 8.4 Hz, 2H), 8.20 (d, J = 8.2 Hz, 2H). 13C NMR (100 MHz, CDCl3,
δ): 122.7 (C), 123.2 (CH), 126.0 (CH), 126.2 (CH), 127.5 (CH), 129.2 (CH), 129.3
(CH), 131.0 (C), 131.6 (C), 132.1 (CH), 133.8 (C), 140.6 (CH), 162.5 (C), 164.6
(CH). MS-ESI (m/z): [M + Na] + calculated for C 34 H 22 Au 2 N 2 Na+, 875.10; found,
875.10. Anal. Calcd for C 34 H 22 Au 2 N 2 : C, 47.90; H, 2.60; N, 3.29. Found: C, 48.48;
H, 2.74; N, 3.10.