| In the past decades, reactions of thiometallate anions [MExS4-x]2- [Cp*MS3]- (M = Mo, W; E =O,S; x = 0-3) with copper(â… ) complexes have been extensively investigated. This is because the resulting Mo(W)/Cu/S clusters possess interesting structural chemistry and various potential applications in biological systems and optoelectronic materials. In this thesis, the third family of synthons [Et4N][Tp*WS3] (1a) and [Et4N][TpMoSS4] (1b) (Tp* = Hydridotris(3,5-dimethylpyrazol-1-yl)borate; Tp = Hydridotris(pyrazol-1-yl)borate) were used to react with Cu(â… ) complexes, and fifteen clusters were isolated therefore. Furthermore, the obtained cubane like core and butterfly-shaped core precursors were chose to react with P- and N-donor ligands to afford another twelve clusters. Among them, six compounds were cluster-based supramolecular assemblies. The main results were briefly summarized as follows:1.Stepwise reactions of [Et4N][Tp*WS3] (1a) with CuBr, CuCN, and CuNCS afforded ten addition products:[Et4N][Tp*W(μ-S)2S(CuBr)](2), [Et4N][Tp*W(μ-S)2(μ3-S)(CuBr)2](3), [Et4N][Tp*W(μ3-S)3(CuBr)3](4), [Et4N][(Tp*W(μ-S)2OCu)2(μ-CN)]·CH3CN(5·CH3CN), [Tp*W(μ-S)2(μ3-S)(CuCN)2·ClCH2CH2Cl]n(6·ClCH2CH2Cl), [Et4N][Tp*W(μ-S)2(μ3-S)(CuCN)2]·CHCl3(7·CHCl3), [Et4N][Tp*WS(μ-S)2(CuNCS)]·0.5CH2Cl2(8·0.5CH2Cl2), [Et4N][Tp*W(μ3-S)(μ-S)2(CuNCS)2]·ClCH2CH2Cl(9·ClCH2CH2Cl), [Et4N]2[Tp*W(μ3-S)3(CuNCS)3(μ3-Br)·1.5ani(10·1.5ani), {[Et4N][Tp*W(μ3-S)3(Cu-μ-SCN)3(Cu-μ3-NCS)]}n(11).From this synthetic strategy, the third-order NLO performances of 8-11, relative to those of 1a, were improved. In addition, 8-11 were observed to show enhanced NLO performances with increasing the number of copper atoms in their frameworks.2. A new set of monomeric, dimeric and polymeric W/Cu/S clusters from a precursor cluster [Et4N][Tp*W(μ3-S)3(CuBr)3] (4) and various N-donor ligands was reported: [Tp*W(μ3-S)3Cu3(py)3(μ3-Br)](PF6)(12),[{Tp*W(μ3-S)3(CuBr)3}(μ6-Br){Tp*W(μ3-S)3Cu3(ani)3}]·4ani·0.5Et2O(13·4ani·0.5Et2O), {[Tp*W(μ3-S)3Cu3(4,4'-bipy)3(μ3-Br)](PF6)·H2O}n(14),[{Tp*W(μ3-S)3Cu3Br2}2(bpee)]·0.5CH2Cl2(15·0.5CH2Cl2), {[{Tp*W(μ3-S)3Cu3(μ3-Br)}2(bpe)3](PF6)2·MeCN}n(16), ([Tp*W(μ3-S)3Cu3Br(μ3-Br)(bpp)]·DMF}n(17). Among them, 14 is a 2D (6,3) cationic network; and 16,17 are 1D zigzag cationic chain and 1D spiral chain, respectively. The NLO performances and electrospary mass spectroscopy of 12-17 were also investigated.3.Reactions of the preformed butterfly cluster [Et4N][Tp*W(μ3-S)(μ-S)2(CuSCN)2](9) with three kinds of N-donor ligand (py, 4,4'-bipy or bpp) led to the formation of three neutral [Tp*W(μ3-S)(μ-S)2Cu2]-based compounds [Tp*W(μ3-S)(μ-S)2Cu2(SCN)(py)2](18), [{Tp*W(μ3-S)(μ-S)2Cu2(SCN)}2(4,4'-bipy)]·3.5H2O(19·3.5H2O), and [Tp*W(μ3-S)(μ--S)2Cu2(SCN)(bpp)]2(20), respectively. The NLO performances of 18-20 were also studied.4.Utilization of the redundant sulfur atoms of 1b itself and halide atom in CuX to synthesis the high nuclearity Mo/Cu/S clusters. Treatment of 1b with three equiv. of CuX in MeCN gave rise to four compounds [Et4N][TpMo(μ3-S)3Cu3Cl2(μ3-Cl)(MeCN)]·MeCN(21·MeCN), [Et4N]2[TpMo(μ3-S)3(CuBr)3(μ3-Br)]·0.75MeCN·0.125MeOH(22·0.75MeCN·0.125MeOH), [Et4N][{TpMo(μ3-S)3Cu3Br}2(μ4-Br)(μ-Br)2]·4H2O(23·4H2O),[Et4N]2[{TpMo(μ3-S)3Cu3I(μ4 -I)}2Cu(μ-I)3]·3.5MeCN(24·3.5MeCN). The analogous reactions performed in pyridine afforded three tetracubane-type clusters (PyH){[{TpMo(μ3-S)3Cu3}4(μ3- S)4](μ12-X)}·Et2O(X=Cl, 25a·Et2O;Br,25b·Et2O;I,25c·Et2O). In the cases of 25a-c, the redundant sulfide atoms of 1b and halide in CuX worked together to bond the basic cluster fragments into tetracubane-like clusters.5.Reactions of the preformed complete cubane core cluster [Et4N]2[TpMo(μ3-S)3(CuBr)3(μ3-Br] (22) with PPh3, aniline, and bpp afforded three compounds [Et4N][TpMo(μ3-S)3(CuBr)3(PPh3)]·CH2Cl2(26·CH2Cl2),[Et4N][TpMo(μ3-S)3(CuBr)3(ani)]·2ani (27·2ani), and {[TpMoCu3Br2(bpp)(μ3-S)3](DMSO)2(H2O)2(CH3OH)0.5}n(28). Among them, 28 is a 1D zigzag supramolecular compound.6.Treatment of dinuclear precursor [Et4N]2[(edt)2Mo2S2(μ-S)2] with CuBr in the presence of py and dppm afforded two symmetric and two asymmetric clusters [Et4N]2[(edt)2Mo2(μ-S)3(μ3-S)Cu]2·2CH2Cl2(29·2CH2Cl2),[Mo2O2(μ-S)2(edt)2Cu2(dppm)2](30), [(edt)2Mo2O(μ3-S)(μ-S)2Cu2(Py)4](31), and [Mo2(μ-S)2(μ3-S)2(edt)2Cu2(dppm)(Py)]·Py(32·Py). Among these obtained clusters, 30 and 31 have internal mirror symmetry or pseudo mirror symmetry; 29 and 32 are asymmetric clusters with racemic formations.
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