新型mo(w)s配体与cu(i)的反应性研究-study on the reactivity of new mo ( w ) s ligand with cu ( i ).docxVIP

Reaction of Novel Mo(W)/S Ligands with Cu(I)AbstractReaction of Novel Mo(W)/S Ligands with Cu(I)AbstractThe chemistry of Mo(W)/Cu/S cluster-based complexes are well known for their numerous structures and diverse applications in optical materials and catalysis. We have been focused on the assembly of thiometallate precursors [MExS4-x]2-, [Cp*MS3]- (M =Mo, W; E = O, S; x = 0-3), [Tp*WS3]- (Cp* = η5-C5Me5; Tp* =hydridotris(3,5-dimethylpyrazol-1-yl)borate) with copper(I) and bridging ligands to form a variety of supramolecular clusters. Some coordination polymers have shown enhanced third-order nonlinear optical (NLO) performances compared to the corresponding precursors.In this thesis, we carried out the researches on the reactions of two precursors [Et4N][Tp*MoS(S4)] (1) and [Et4N][Tp*W2S8] (2) with Cu(I) and Ag(I) salts, and successfully isolated 10 new clusters. These results were briefly summarized as follows:Reactions of [Et4N][Tp*MoS(S)4] (1) with 3 equiv. of CuX (X = Cl, Br, I, CN) or [Cu(MeCN)4]ClO4 in CH2Cl2/MeCN or CH2Cl2/DMF afforded [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (3), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (4: X = Br; 5: X = I), [Et4N][Tp*MoO(μ-S)2(CuX)] (6: X = I; 7: X = CN) and[Tp*Mo(μ3-S)3Cu3(μ3-S’)]4 (8). Compounds 3–8 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, electrospray ion mass spectra (ESI-MS) and X-ray crystallography. The cluster dianion of 3 has a complete cubane-like [Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] structure while the anion of 4 or 5 consists of an incomplete cubane-like [Tp*Mo(μ3-S)3(CuX)3] structure. The anion of 6 or 7 has abinuclear structure in which one [Tp*MoO(μ-S)2] moiety and one CuX unit are linked by a pair of μ-S atoms. The structure of 8 may be considered as a supercube whose eight corners are occupied by four incomplete cubane-like [Tp*Mo(μ3-S)3Cu3] fragments and four μ3–S’ atoms. The third-order nonlinear optical (NLO) properties of 3–7 in DMF were investigated by femtosecon