Coinage Metal Complexes Supported by the Tri- and Tetraphosphine Ligands

详细信息    查看全文

• 作者：Minh Thuy Dau ; Julia R. Shakirova ; Antti J. Karttunen ; Elena V. Grachova ; Sergey P. Tunik ; Alexey S. Melnikov ; Tapani A. Pakkanen ; Igor O. Koshevoy
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：May 5, 2014
• 年：2014
• 卷：53
• 期：9
• 页码：4705-4715
• 全文大小：581K
• 年卷期：v.53,no.9(May 5, 2014)
• ISSN：1520-510X

文摘

A series of tri- and tetranuclear phosphine complexes of d¹⁰ metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM₂(PPP)₂]³⁺ (M = Au (1), Cu (2), Ag (3)), [M₄(PPPP)₂]⁴⁺ (M = Ag (4), Au (5)), [AuAg₃(PPPP)₂]⁴⁺ (6), and [Au₂Cu₂(PPPP)₂(NCMe)₄]⁴⁺ (7), were characterized crystallographically. The trinuclear clusters 1鈥?b>3 contain a linear metal core, while in the isostructural tetranuclear complexes 4鈥?b>6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated Cu^I ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation鈥揹esolvation. The complexes 1鈥?b>3 and 5鈥?b>7 exhibit room temperature luminescence in the solid state (桅_em = 6鈥?4%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered d_蟽* 鈫?p_蟽 transitions.