Luminescent homo- and heteropolynuclear platinum(II) chalcogenido aggregates based on [Pt2E2 (P∧N)4] units (E = S, Se)

Abstract

A series of homodinuclear platinum(II) complexes containing bridging chalcogenido ligands, [Pt2(μ- E)2(P∧N)4] (P∧N = dppy, E=S (1), Se (2); P∧N = tBu-dppy, E=S (3)) (dppy = 2-(diphenylphosphino)pyridine, tBu-dppy = 4-tert-butyl-2-(diphenylphosphino)pyridine) have been synthesized and characterized. The nucleophilicity of the {Pt2E2} unit towards a number of d10 metal ions and complexes has been demonstrated through the successful isolation of a number of novel heteropolynuclear platinum(II) - copper(I), -silver(I), and -gold(I) complexes: [{Pt2μ3- E)2(dppy)4}2Ag3] (PF6)3 (E = S (4); Se (5)) and [Pt2(dppy)4(μ3-E)2 M2(dppm)]-X2 (E = S, M = Ag, X = BF4 (6); E = S, M = Cu, X = PF6 (7); E = S, M = Au, X = PF6 (8); E = Se, M = Ag, X = PF6 (9); E = Se, M = Au, X = PF6 (10)). Some of them display short metal ⋯ metal contacts. These complexes have been found to possess interesting luminescence properties. Through systematic comparison studies, the emission origin has been probed.