Reactions of [Et4N][Tp*W(μ3-S)(μ-S)2(CuSCN)2] with Nitrogen Donor Ligands: Syntheses, Structures, and Third-Order Nonlinear Optical Properties

Reactions of the preformed cluster [Et4N][TpWμ3SμS2CuSCN2] 1 with pyridine py, 4,4′bipyridine 4,4′bipy, or 1,3bis4pyridylpropane bpp led to the formation of three neutral [TpWμ3SμS2Cu2]based compounds [TpWμ3SμS2Cu2SCNpy2] 2, [{TpWμ3SμS2Cu2SCN}24,4′bipy]·3.5H2O 3·3.5H2O, and [TpWμ3SμS2Cu2SCNbpp]24, respectively. Compounds 2–4were characterized by elemental analysis, IR spectra, UVVis spectra, 1H NMR, and Xray analysis. There are two linkage isomers [TpWμ3SμS2Cu2SCNpy2] and [TpWμ3SμS2Cu2NCSpy2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3has a double butterflyshaped structure in which two [TpWμ3SμS2Cu2SCN] fragments are linked with a single 4,4′bipy bridge. For 4, the two butterflyshaped [TpWμ3SμS2Cu2SCN] fragments are interconnected by a pair of bpp bridges. The thirdorder nonlinear optical NLO performances of 2–4in DMF were also investigated by Zscan techniques.© WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009