Koshevoy et al.
[{Au3Cu2(C2Ph)6}Au3(PPh2C6H4PPh2)3][PF6]2 (3). Complex 2
(120 mg, 0.115 mmol) was dissolved in CH2Cl2 (10 cm3) and
diluted with diethyl ether (5 cm3), and a solution of Cu(NCMe)4PF6
(28 mg, 0.075 mmol) in CH2Cl2 (5 cm3) was added dropwise. A
bright yellow-orange solution was stirred for 30 min in the absence
of light. Solvents were removed on a rotary. A yellow-orange solid
was recrystallized by the gas-phase diffusion of pentane into its
acetone solution at 5 °C to give orange plate crystals (119 mg,
87%). ES MS (m/z): [Au6Cu2(C2Ph)6(PPh2C6H4PPh2)3]2+, 1627
(calcd 1627). 31P{1H} NMR (acetone-d6; δ): 43.6 (s, 3P), -144.8
{Au(C2Ph)}: 132.22 (s, ortho-C (Ph-Ct C)), 127.84 (s, meta-C
(Ph-Ct C)), 126.70 (s, para-C (Ph-Ct C)), 124.76 (s, ipso-C
(Ph-Ct C)), ca. 104.1 (br (Ph-Ct C)). Anal. calcd for C58H42-
Au2P2: C, 58.30; H, 3.54. Found: C, 58.14; H, 3.74.
[{Cu12Au10(C2Ph)20}Au3(PPh2(C6H4)3PPh2)3][PF6]5 (6). Com-
plex 5 (200 mg, 0.168 mmol) was dissolved in CH2Cl2 (10 cm3),
and a solution of Cu(NCMe)4PF6 (41 mg, 0.201 mmol) in acetone
(6 cm3) was added dropwise. A bright red-orange solution was
stirred for 30 min in the absence of light and diluted with heptane
(5 cm3), and solvents were removed on a rotary evaporator. A red
residue was extracted with an acetone/heptane mixture (3:1 v/v, 4
× 8 cm3) to leave a pale insoluble material. Solvents were
evaporated, and extraction was repeated with the same solvent
mixture. Subsequent recrystallization from a CH2Cl2 solution at 5
°C by gas-phase diffusion of the pentane gave red crystals and a
nearly colorless solid, the majority of which was mechanically
removed. The product, 6, was extracted with an acetone/heptane
mixture (3:1 v/v, 4 × 8 cm3) to leave some pale insoluble material.
Solvents were evaporated to give a red microcrystalline powder.
Final recrystallization under the conditions mentioned above gave
a red crystalline solid (95 mg, 47% based on Au). 31P{1H} NMR
1
(sept, 1P, PF6). H NMR (acetone-d6; δ), {Au(C2Ph)2}: 6.75 (dd,
H-ortho, 12H, J(H-H) 8.2, 1.3 Hz), 6.83 (dd, H-meta, 12H,
J(H-H) 7.5, 8.2 Hz), 7.13 (tt, H-para, 6H, J(H-H) 7.5, 1.3 Hz).
Diphosphine: 7.98 (dm(AXX′), H-ortho, 24H, J(H-H) 8.2, J(P-H)
13.4 Hz), 7.76 (m(A2X2), {P-C6H4-P} 12H, <J(P-H)> 3.6 Hz),
7.65 (t, H-para, 12H, J(H-H) 7.5 Hz), 7.45 (dm(AXX′), H-meta,
24H, J(H-H) 8.2, 7.5 Hz). 13C NMR (acetone-d6; δ), {Au(C2Ph)2}:
133.76 and 129.87 (s, C-ortho and C-meta), 129.47 (s, C-para),
125.33 (s, C-ipso), 114.54 (s, Ct C-Au), 112.69 (s, Ct C-Au).
Diphosphine: 137.37 (m (AXX′), C (-C6H4-), J(P-C) 58.8 Hz),
137.04 (m (AXX′), C-ortho, J(P-C) 16.5 Hz), 135.64 (m (AXX′),
C(H) (-C6H4-), J(P-C) ca. 11 Hz), 134.61 (s, C-para), 131.70
(s, C-meta), 129.84 (m (AXX′), C-ipso, J(P-C) 55.5 Hz). Anal.
calcd for C138H102Au6Cu2F12P8: C, 46.76; H, 2.90. Found: C, 46.92;
H, 3.30.
1
(acetone-d6; δ): 42.8 (s, 6P), -144.8 (sept, 5P, PF6). H NMR
(acetone-d6; δ), diphosphine: 8.47 (s, -C6H4-, 12H), 8.375 (d,
meta-H, (-C6H4-P), 12H, J(H-H) 8.3 Hz), 7.80 (dm (AXX′),
ortho-H, (-C6H4-P), 12H, J(H-H) 8.3, J(P-H) 6.3 Hz), 7.66 (dm
(AXX′), ortho-H, (Ph-P), 24H, J(H-H) 8.4, J(P-H) 6.8 Hz), 7.60
(t, para-H, (Ph-P), 12H, J(H-H) 7.5 Hz), 7.34 (dd, meta-H,
(Ph-P), 24H, J(H-H) 8.4, 7.5 Hz). {Au(C2Ph)2} rods (three set
of rods A/B/C ) 1:3:6 for numbering scheme, see text), A: 7.30
(d, ortho-H, 4H, J(P-H) 8.1 Hz), 7.21 (t, para-H, 2H, J(P-H) 7.7
Hz), 6.19 (dd, meta-H, 4H, J(P-H) 7.7, 8.1 Hz). B: 7.19 (t, para-
H, 6H, J(P-H) 7.5 Hz), 6.81 (dd, meta-H, 12H, J(P-H) 7.5, 8.1
Hz), 6.23 (d, ortho-H, 12H, J(P-H) 8.1 Hz). C: 7.11 (t, para-H,
12H, J(P-H) 7.6 Hz), 6.85 (d, ortho-H, 24H, J(P-H) 8.3 Hz),
6.64 (dd, meta-H, 24H, J(P-H) 7.6, 8.3 Hz). 13C NMR (acetone-
d6; δ), diphosphine: 144.53 (s, para-C (P-C6H4)), 140.73 (s, C
(-C6H4-)), 136.73 (m (AXX′), ortho-C, (P-C6H4), J(P-C) 14.4
Hz), 136.53 (m (AXX′), ortho-C, (P-Ph), J(P-C) 15.6 Hz), 134.5
(s, para-C, (P-Ph)), 131.57 (m (AXX′), meta-C, (P-C6H4), J(P-C)
11.8 Hz), 130.26 (s, CH (-C6H4-)), 129.73 (m (AXX′), ipso-C,
(P-Ph), J(P-C) 57.6 Hz), 129.68 (m (AXX′), meta-C, (P-C6H4),
J(P-C) 11.0 Hz), 129.67 (m (AXX′), ipso-C, (P-C6H4), J(P-C)
59.5 Hz). {Au(C2Ph)2} rods (three set of rods A/B/C ) 1:3:6 for
numbering scheme see text), A: 135.92 (s, ortho-C), 133.80 (s, para-
C), 131.01 (s, meta-C), 120.67 (s, ipso-C), 120.03 (s, Ct C-Au),
98.70 (s, Ct C-Au). B: 134.44 (s, ortho-C), 130.68 (s, para-C),
130.03 (s, meta-C), 123.46 (s, ipso-C), 120.72 (s, Ct C-Au),
107.53 (s, Ct C-Au). C: 134.97 (s, ortho-C), 132.38 (s, para-C),
130.38 (s, meta-C), 124.94 (s, Ct C-Au), 121.40 (s, ipso-C),
101.50 (s, Ct C-Au). Anal. calcd for C286H196Au13Cu12F30P11: C,
43.67; H, 2.51. Found: C, 43.69; H, 2.68.
Photophysical Measurements. An Excimer laser, LPX 100
(Lambda Physik), and light-emitting diode (LED; maximum
emission at 470 nm) were used to pump luminescence. The laser
pulse width was 35 ns; pulse energy, 160 mJ; and repetition rate,
1-25 Hz. A LED was used in the continue and pulse mode (pulse
width, 1-20 µs; duty of edge, ∼90 ns; repetition rate, 100 Hz to
10 kHz). A digital oscilloscope, Tektronix TDS3014B (Tektronix,
bandwidth 100 MHz), and photodiode with a 10 ns time resolution
were used for lifetime measurements. Emission spectra were
recorded using an HR2000 spectrometer (Ocean Optics). A halogen
lamp, LS-1-CAL (Ocean Optics), and deuterium lamp, DH2000
(Ocean Optics), were used to calibrate the absolute spectral response
4,4′′-Bis(diphenylphosphino)-terphenyl (4). 4,4′′-Dibromoter-
phenyl (1 g, 2.6 mmol) was suspended in THF (60 cm3); the
suspension was cooled to -70 °C, and a 1.6 M solution of n-BuLi
in hexanes (4.5 mL, 7.2 mmol) was added within 5 min. The
reaction mixture was slowly (ca. 4 h) warmed to -10 °C, stirred
at this temperature for 1 h more, and then cooled again to -70 °C,
and neat PPh2Cl (1.55 g, 7.0 mmol) was added dropwise. The
cooling bath was removed; the reaction mixture was allowed to
reach room temperature and was stirred overnight. Then, it was
filtered; volatiles were evaporated, and an oily yellow residue was
thoroughly washed with methanol (4 × 30 cm3) to give a white
solid that was recrystallized from CHCl3/methanol (1.0 g, 65%).
ES MS (m/z): [M+] 598 (calcd 598). 31P{1H} NMR (CDCl3; δ):
1
-5.6 (s). H NMR (CDCl3; δ): 7.68 (s, 4H, -C6H4-), 7.62 (dd,
J(H-H) 8.2, J(P-H) 1.5 Hz, 4H, -C6H4-P), 7.41 (dd, J(H-H)
8.2, J(P-H) 7.5 Hz, 4H, -C6H4-P), 7.39-7.36 (m, 20H, Ph2P).
Anal. calcd for C42H32P2: C, 84.26; H, 5.39. Found: C, 83.98; H,
5.34.
4,4′′-(PhC2AuPPh2)2(C6H4)3 (5). (AuC2Ph)n (110 mg, 0.369
mmol) was suspended in CH2Cl2 (10 cm3). Complex 4 (115 mg,
0.192 mmol) was added, and the yellow suspension turned into a
colorless transparent solution within minutes. It was diluted with
toluene (10 cm3) and stirred for 30 min in the absence of light.
The resulting solution was passed through Al2O3 (0.5 × 2 cm,
neutral, ∼150 mesh) and concentrated to ca. 5 cm3. A white
microcrystalline solid was precipitated by centrifugation, washed
with toluene (5 cm3) and diethyl ether (2 × 5 cm3), and vaccuum-
dried. Yield: 205 mg (93%). An analytically pure sample was
obtained by recrystallization from CH2Cl2/toluene. 31P{1H} NMR
1
(CDCl3; δ): 41.3 (s). H NMR (CDCl3; δ): 7.74-7.46 (m, 36H),
7.30-7.15 (m, 6H). 13C{1H} NMR (CDCl3; δ), diphosphine:
143.37 (d, C(-C6H4-), J(P-C) 2.4 Hz), 139.24 (d, para-
C(-C6H4-P), J(P-C) 1.3 Hz), 134.74 (d, ortho-C(-C6H4-P),
J(P-C) 14.1 Hz), 134.17 (d, ortho-C(Ph-P), J(P-C) 13.9 Hz),
131.55 (d, para-C(Ph-P), J(P-C) 2.4 Hz), 129.58 (d, ipso-
C(Ph-P), J(P-C) 56.1 Hz), 129.10 (d, meta-C(Ph-P), J(P-C)
11.4 Hz), 128.57 (d, ipso-C(-C6H4-P), J(P-C) 56.5 Hz), 127.73
(s, CH(-C6H4-)), 127.51 (d, meta-C(-C6H4-P), J(P-C) 11.6 Hz).
9480 Inorganic Chemistry, Vol. 47, No. 20, 2008