847974-95-2Relevant academic research and scientific papers
Structural variations and spectroscopic properties of luminescent mono- and multinuclear silver(I) and copper(I) complexes bearing phosphine and cyanide ligands
Lin, Yong-Yue,Lai, Siu-Wai,Che, Chi-Ming,Fu, Wen-Fu,Zhou, Zhong-Yuan,Zhu, Nianyong
, p. 1511 - 1524 (2005)
Reaction of equimolar amounts of AgCN and PCy3 gave the polymer [(Cy3P)Ag(NCAgCN)]∞ (1), whereas employment of excess PCy 3 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(μ-dcpm)2][Ag-(CN)2]2· (CH3OH)2 (3a·(CH3OH)2) and [Ag2(μ-dcpm)2][Ag(CN)2]2 (3b), respectively. The similar reaction of CuCN with PCy3 afforded the polymeric compound [{(Cy3P)Cu(CN)}3]∞ (4), whereas treatment of CuCN with dcpm gave [Cu2(μ-dcpm)2(CN) 2] (5). Employment of diphosphine ligands with longer -(CH 2)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)(μ-dcpe)]PF6 (6(PF6)) and [{Cu(dppp)}3(CN)2(μ-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 (ε = 350 dm3 mol-1 cm-1). For 3a, 3b, and 5, the intense absorption bands at λmax = 257-276 nm with ε values of (1.73-1.80) × 104 dm3 mol -1 cm-1 are assigned to [ndσ* → (n + 1)pσ] transitions. Complexes 3a and 3b emit at λmax = 365 nm in CH3CN (quantum yield ～6 × 10-3, lifetime ～0.2 μs). The solid-state emission of 5 (λmax = 470 and 488 nm at 298 and 77 K) is red-shifted in energy from that of 4 (λmax = 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 λmax at 382-416 nm, which is assigned to the [3d → (4s, 4p)] triplet excited state.
