Syntheses And Third-Order NLO Properties Of W/Cu/S Clusters Containing [Tp^*WS₃](Tp^*=Hydridotris(3, 5-dimethylpyrazol-1-yl) Borate)

W/Cu/S clusters have been extensively investigated because of their structure diversity, broad application prospects in industrial catalysis and optical materials. However, studies in this respect are somewhat underdeveloped by their limited solubility in solvents. It is therefore urgent to screen out new kinds of proper precursors that possess good solubility. A trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et4N][Tp*WS3] (1) works for this purpose due to its bulky Tp*. When it reacted with transition metal complexes, it may form soluble clusters. In addition, to our knowledge, the chemistry and third-order nonlinear optical properties of W/Cu/S clusters containing [Tp*WS3] unit have not been explored yet. This dissertation was focused on: i) the reactions of compound 1 with CuX (X = Br, Cl, NCS, or CN): isolation, structures, and third-order NLO properties; ii) the reactions of the W/Cu/S precursors containing [Tp*WS3Cu3] unit with donor ligands such as PPh3, 1,2-bis(diphenyl-phosphino)ethane (dppe), bis(diphenyl-phosphino)methane (dppm).Reactions of 1 with CuX (X = Br, Cl, NCS, CN) afforded six heterometallic clusters. Treatment of 1 with 2 equiv of CuBr in CH2Cl2 produced a trinuclear butterfly-shaped anionic cluster [Et4N][Tp*W(μ3-S)(μ-S)2(CuBr)2] (2). Reactions of 1 with 3 equiv of CuBr or CuCl in CHCl3 generated tetranuclear incomplete-cubane anionic clusters [Et4N][Tp*W(μ3-S)3(CuX)3] (X = Br (3), X = Cl (4)). Reactions of 1 with 3 equiv of CuNCS in MeCN yielded a neutral decanuclear cluster [Tp*W(μ3-S)3Cu3(μ-NCS)3(CuMeCN)]2 (5) as a major product and a binuclear anionic cluster [Et4N][Tp*WO(μ-S)2(CuNCS)] (6) as a minor product. Solvothermal reactions of 1 with 3 equiv of CuCN in MeCN at 80 oC for 48 h followed by slowly cooling it to ambient temperature gave rise to a 1D spiral polymeric cluster [Tp*W(μ3-S)(μ-S)2Cu2(MeCN)(μ-CN)]∞(7). In addition, 1 and 5 exhibited good third-order NLO performances in MeCN under the femtosecond measurement. Their third-order nonlinear optical susceptibilityχ(3) and second-order hyperpolarizabilityγvalues were measured to be 0.38×10-14 esu and 1.07×10-32 esu (1), 1.00×10-14 esu and 5.46×10-32 esu (5), respectively.The terminal Cl in [Et4N][Tp*W(μ3-S)3(CuBr)3] (3) can be easily substituted by donor ligands such as PPh3, dppm or pyridine, bipyridine. Reaction of 3 with excess PPh3 in MeCN yielded a trinuclear neutral compound [Tp*W(μ3-S)(μ-S)2Cu2Br(PPh3)] (8), while that of 3 with excess dppe in DMF afforded a neutral binuclear compound [Tp*WS(μ-S)2Cu(dppe)] (9). On the other hand, reaction of 3 with dppm afforded [Et4N][Tp*W(μ3-S)(μ-S)2(CuBr)2] (2) without dppm ligands being coordinated at copper centers, while that of 5 with dppm produced a neutral trinuclear compound [Tp*W(μ3-S)(μ-S)2Cu2(NCS)(dppm)] (10). Compounds 8-10 were all characterized by IR, elemental analysis and their structures were determined by X-ray analysis.