Self-assembly of luminescent Sn(IV)/Cu/S clusters using metal thiolates as metalloligands

Through the use of (Bu4N)2[Sn3S4(edt)3] (edt=SCH2CH2S(2-)) 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).3H 2O (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 SnS 5 dreich trigonal bipyramid sharing one vertex and two sides with two slightly distorted CuS 2P2 tetrahedrons. Compound 2 has a linear [(Ph3P)Cu]2Sn(SPh)6 cluster that is composed of a central distorted SnS 6 octahedron sharing two opposite planes with two slightly distorted CuS 3P tetrahedrons. Compound 1a exhibited an emission at 568 nm (tau=12.86 micros) in the solid state, while in CH 2Cl 2 solution, 1a exhibited a green emission at 534 nm (tau=4.75 micros). Compound 2 showed an intense red emission at 696 nm (tau=3.64 micros) upon excitation at 307 nm in the solid state.