2.7 Experimental Section
37
To chlorogold(I) isocyanide complex 5 (0.334 g, 0.5 mmol) in 100 mL flask,
THF (2 ml) was added under nitrogen atmosphere. After cooling to 0 °C, organozinc
iodide reagent 4 in THF (1.10 ml, 1.2 mmol) was added to the mixture dropwise and
stirred for 2 h [23]. The reaction was quenched by addition of a phosphate buffer
solution and then extracted with CH 2 Cl 2 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 flash column chromatography (SiO 2 ,
CHCl 3 /hexane = 6:1) gave a yellow and light blue solid mixture. The resulting solid
was dissolved in CHCl 3 at 50 °C and stand in a refrigerator for 24 h, affording a light
blue crystal. The resulting crystal contains CHCl 3 (approx. 1.0 equiv as indicated by
1 H NMR in CD 2 Cl 2 ), thus denoted as 3/CHCl 3 . Ball milling of 3/CHCl 3 for 40 min
at 4600 rpm gave an analytically pure yellow powder 3 ground (0.177 g, 0.23 mmol,
47%).
1 H NMR (400 MHz, CD 2 Cl 2 , δ): 6.98 (tt, J = 1.5 Hz, 7.5 Hz, 2H), 7.12 (t, J
= 7.6 Hz, 4H), 7.29 (dd, J = 1.4 Hz, 7.8 Hz, 4H), 7.52 (dd, J = 0.8 Hz, 8.0 Hz, 2H),
7.59–7.74 (m, 6H).
13 C NMR (100 MHz, CDCl 3 , δ): 124.0 (C), 126.2 (CH), 127.6
(CH), 128.7 (CH), 130.8 (CH), 131.1 (CH), 131.7 (CH), 133.9 (C), 141.0 (CH),
162.7 (C), 164.3 (C). MS-ESI (m/z): [M + Na]
+ calculated for C 26 H 18 Au 2 N 2 Na,
775.0699; found, 775.0699. Anal. Calcd for C 26 H 18 Au 2 N 2 : C, 41.51; H, 2.41; N,
3.72. Found: C, 41.21; H, 2.42; N, 3.66.
2.7.3 Optical Properties of 3 in Solution Phase
See Figs. 2.14 and 2.15.
600
500
400
300
200
λ / nm
Normalized intensity
475
4
5
2
1
6
2
0
1
2
3
4
ε / 10 5
M -1
cm -1
Fig. 2.14 UV/vis absorption (dashed black line), excitation (dashed green line, λ em = 475 nm),
and emission spectra (solid green line, λ ex = 261 nm) of 3 in CHCl 3 (c = 3.6 × 10 −5 M) at room
temperature
37
To chlorogold(I) isocyanide complex 5 (0.334 g, 0.5 mmol) in 100 mL flask,
THF (2 ml) was added under nitrogen atmosphere. After cooling to 0 °C, organozinc
iodide reagent 4 in THF (1.10 ml, 1.2 mmol) was added to the mixture dropwise and
stirred for 2 h [23]. The reaction was quenched by addition of a phosphate buffer
solution and then extracted with CH 2 Cl 2 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 flash column chromatography (SiO 2 ,
CHCl 3 /hexane = 6:1) gave a yellow and light blue solid mixture. The resulting solid
was dissolved in CHCl 3 at 50 °C and stand in a refrigerator for 24 h, affording a light
blue crystal. The resulting crystal contains CHCl 3 (approx. 1.0 equiv as indicated by
1 H NMR in CD 2 Cl 2 ), thus denoted as 3/CHCl 3 . Ball milling of 3/CHCl 3 for 40 min
at 4600 rpm gave an analytically pure yellow powder 3 ground (0.177 g, 0.23 mmol,
47%).
1 H NMR (400 MHz, CD 2 Cl 2 , δ): 6.98 (tt, J = 1.5 Hz, 7.5 Hz, 2H), 7.12 (t, J
= 7.6 Hz, 4H), 7.29 (dd, J = 1.4 Hz, 7.8 Hz, 4H), 7.52 (dd, J = 0.8 Hz, 8.0 Hz, 2H),
7.59–7.74 (m, 6H).
13 C NMR (100 MHz, CDCl 3 , δ): 124.0 (C), 126.2 (CH), 127.6
(CH), 128.7 (CH), 130.8 (CH), 131.1 (CH), 131.7 (CH), 133.9 (C), 141.0 (CH),
162.7 (C), 164.3 (C). MS-ESI (m/z): [M + Na]
+ calculated for C 26 H 18 Au 2 N 2 Na,
775.0699; found, 775.0699. Anal. Calcd for C 26 H 18 Au 2 N 2 : C, 41.51; H, 2.41; N,
3.72. Found: C, 41.21; H, 2.42; N, 3.66.
2.7.3 Optical Properties of 3 in Solution Phase
See Figs. 2.14 and 2.15.
600
500
400
300
200
λ / nm
Normalized intensity
475
4
5
2
1
6
2
0
1
2
3
4
ε / 10 5
M -1
cm -1
Fig. 2.14 UV/vis absorption (dashed black line), excitation (dashed green line, λ em = 475 nm),
and emission spectra (solid green line, λ ex = 261 nm) of 3 in CHCl 3 (c = 3.6 × 10 −5 M) at room
temperature