Synthesis, Conformation And Character Of W/Cu/S Supermolecule Clusters Containing Tp~* Group

In the past decades, the Mo(W)/Cu/S clusters possess interesting structural chemistry and various potential applications in biological systems and optoelectronic materials. In the former reports, reactions of thiometallate anions [AMo(W)S₃]- (A = O, S, Cp^*) with copper(Ⅰ) complexes have been extensively investigated. In recent years, a kind of new type Mo(W)/Cu/S cluster containing Tp^* group draw our attention due to their good solubility and special steric effect. Although compounds containing Tp^* group have carried on a series of study, we carry on further research for enriching those clusters and searching for better NLO materials. In this thesis, we focused on:ⅰⅱ) the reactions of compound [Et₄N][Tp^*WS₃] (1) with CuX: isolation, structures, and obtain five different-shaped core clusters;ⅱ) the reactions of the W/Cu/S precursor [Et₄N][Tp^*WS₃(CuBr)₃] (2) unit with different N-donor ligands and to afford another four clusters. Among them, two compounds were cluster-based supramolecular assemblies. The main results were briefly summarized as follows:1. Reactions of [Et₄N][Tp^*WS₃] (1) with CuI, CuNCS and Cu(CH₃CN)₄ClO₄ afforded five addition products :[Et₄N][Tp^*W(μ2-S)₂OCuCl] (3), [Et₄N][Tp^*W(μ2-S)₃(CuI)₂]·CH₂Cl₂ (4), [Et₄N][Tp^*W(μ₃-S)₃(CuI)₃] (5), [Tp^*W(μ2-S)₂(μ₃-S)Cu(μ2-SCN)(CuCH₃CN)]2 (6), [{Tp^*W(μ₃-S)₃Cu₃(CH₃CN)₃}₂(μ6-Cl)](ClO₄)₂ (7). Among them, compound 3 is [1+1] product with a MCu-ring structure; Compound 4 is [1+2] product with a butterfly-shaped MCu2 structure; Compound 5 is [1+3] product with an incomplete cubane-like MCu₃ structure; Compound 6 is [1+2] product with double butterfly-shaped MCu2 structure; Compound 7 is [1+3] product with double complete cubane-like MCu₃ structure.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] (2) and three N-donor ligands (including monodentate ligandα-MePy, bidentate ligand 1,4-pyz and tridentate ligand MA) was reported: [Tp^*W(μ₃-S)₃Cu₃(α-MePy)₃(μ₃-Br)](PF₆)·0.5CH₂Cl₂ (8·0.5CH₂Cl₂), {[Tp^*W(μ₃-S)₃Cu₃(1,4-pyz){(1,4-pyz)_0.5}₂(μ₃-Br)][Tp^*WS₃(CuBr)₃]}n (9) , {[Tp^*W(μ₃-S)₃Cu₃Br(μ₃-Br)₂(MA)₂]·2CH₃OH}n (10·2CH₃OH) , {[Tp^*WS₃Cu₃Br(μ₃-Br)(MA)₂]·CH₃CN·0.5Et₂O} (11·CH₃CN·0.5Et₂O). Among them, 8·0.5CH₂Cl₂ and 11·CH₃CN·0.5Et₂O are a monomer structure; The cation of compound 9 is a 1D zigzag chain, while the structure of anion is the same to 2; 10·2CH₃OH is a 1D spiral chain. The NLO performances and electrospary mass spectroscopy of 8-11 were also investigated. The NLO performances of 8-11 were almost the same, which may be attributed to the fact that these clusters are diasscioated into smaller cluster fragments in the solution.