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Lin YY, Lai SW, Che CM, Fu WF, Zhou ZY, Zhu N: Structural variations and spectroscopic properties of luminescent mono- and multinuclear silver (I) and copper (I) complexes bearing phosphine and cyanide ligands. Inorg Chem. 2005 Mar 7;44(5):1511-24.
Reaction of equimolar amounts of AgCN and PCy3 gave the polymer [(Cy3P) Ag (NCAgCN)] infinity (1), whereas employment of excess PCy3 yielded the discrete compound [(Cy3P) 2Ag (NCAgCN)] (2). Reacting bis (dicyclohexylphosphino) methane (dcpm) with AgCN in 1:1 and 1:2 molar ratios gave two crystalline forms, namely [Ag2 (mu-dcpm) 2][Ag (CN) 2] 2 x (CH3OH) 2 (3a x (CH3OH) 2) and [Ag2 (mu-dcpm) 2][Ag (CN) 2] 2 (3b), respectively. The similar reaction of CuCN with PCy3 afforded the polymeric compound [{(Cy3P) Cu (CN)}3] infinity (4), whereas treatment of CuCN with dcpm gave [Cu2 (mu-dcpm) 2 (CN) 2] (5). Employment of diphosphine ligands with longer -(CH2) n- spacers, such as 1,2-bis (dicyclohexylphosphino) ethane (dcpe, n = 2) and 1,3-bis (diphenylphosphino) propane (dppp, n = 3), in reactions with [Cu (CH3CN) 4] PF6 and KCN afforded the macrocylic compounds [{Cu (dcpe)}2 (CN)(mu-dcpe)] PF6 (6 (PF6)) and [{Cu (dppp)}3 (CN) 2 (mu-dppp)] PF6 (7 (PF6)), respectively. The hexanuclear complex [Cu (CN)(PCy3)] 6 (8) was obtained by reacting CuCN with PCy3 in the presence of sodium pyridine-2-thiolate. The UV-vis absorption spectrum of 1 in acetonitrile displays a weak shoulder at 245 nm (epsilon = 350 dm3 mol (-1) cm (-1)). For 3a, 3b, and 5, the intense absorption bands at lambdamax = 257-276 nm with epsilon values of (1.73-1.80) x 10 (4) dm3 mol (-1) cm (-1) are assigned to [ndsigma --> (n + 1) psigma] transitions. Complexes 3a and 3b emit at lambdamax = 365 nm in CH3CN (quantum yield approximately 6 x10 (-3), lifetime approximately 0.2 micros). The solid-state emission of 5 (lambdamax = 470 and 488 nm at 298 and 77 K) is red-shifted in energy from that of 4 (lambdamax = 401 and 405 nm at 298 and 77 K, respectively). In 77 K MeOH/EtOH (1:4) glassy solution, complexes 4-8 display intense emission with lambdamax at 382-416 nm, which is assigned to the [3d --> (4s, 4p)] triplet excited state. |
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