Self-Assembly of Luminescent Sn(IV)/Cu/S Clusters Using Metal Thiolates as Metalloligands

Through the use of (Bu4N)2[Sn3S4(edt)3] (edt = SCH2CH2S2−) and Sn(SPh)4 as metalloligands, three neutral compounds have been obtained: [(Ph3P)2Cu]2SnS(edt)2·2CH2Cl2·H2O (1a), [(Ph3P)2Cu]2SnS(edt)2·2DMF·H2O (1b), and [(Ph3P)Cu]2Sn(SPh)6·3H2O (2). Single-crystal X-ray diffraction studies revealed that compounds 1a and 1b contain the same neutral butterfly-like [(Ph3P)2Cu]2SnS(edt)2 cluster, which consists of one central SnS5 dreich trigonal bipyramid sharing one vertex and two sides with two slightly distorted CuS2P2 tetrahedrons. Compound 2 has a linear [(Ph3P)Cu]2Sn(SPh)6 cluster that is composed of a central distorted SnS6 octahedron sharing two opposite planes with two slightly distorted CuS3P tetrahedrons. Compound 1a exhibited an emission at 568 nm (τ = 12.86 µs) in the solid state, while in CH2Cl2 solution, 1a exhibited a green emission at 534 nm (τ = 4.75 µs). Compound 2 showed an intense red emission at 696 nm (τ = 3.64 µs) upon excitation at 307 nm in the solid state.