Luminescent Alkynyl Platinum−Cadmium Complexes: Structural Characterization of an Unusual Decanuclear Cluster [Pt4Cd6(C⋮CPh)4(μ-C⋮CPh)12(μ3-OH)4]

The reaction of (NBu(4))(2)[Pt(C triple bond CPh)(4)] with Cd(ClO(4))(2).6H(2)O in a 1:1 molar ratio yields a white solid [PtCd(C triple bond CPh)(4)](n) 1 (75% yield) together with yellow crystals of a very unusual decanuclear platinum-cadmium cluster [Pt(4)Cd(6)(C triple bond CPh)(4)(mu-C triple bond CPh)(12)(mu(3)-OH)(4)] 2 in low yield. Slow diffusion of acetonic solutions of the starting materials under aerobic conditions only produces crystals of 2 which have been shown by an X-ray analysis to be composed of a big hexanuclear cation [Cd(6)(mu(3)-OH)(4)](8+) and four [Pt(C triple bond CPh)(4)](2-) anions, held together by Pt.Cd and pi.Cd acetylide interactions. On the other hand, treatment of the insoluble product 1 with 1 equiv of NBu(4)X yields tetranuclear mixed-metal soluble complexes (NBu(4))(2)[[Pt(mu-C triple bond CPh)(4)](2)(CdX)(2)] (X = Cl A, Br 3, CN 4), which contain two platinate fragments connected by two CdX units through Pt.Cd and mainly Cd.C(alpha) interactions. All complexes are strongly emissive in the solid state at room temperature.