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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) 2Ag (CN) 22 x (CH3OH) 2 (3a x (CH3OH) 2) and Ag2 (mu-dcpm) 2Ag (CN) 22 (3b), respectively. The similar reaction of CuCN with PCy3 afforded the polymeric compound (Cy3P) Cu (CN) 3infinity (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) 4PF6 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.
Lin et al. (Sat,) studied this question.