V(W, Mo)/S/Cu Heterometallic Clusters: Syntheses, Structures And Third-order Nonlinear Optic Properties

The dissertation focuses on the syntheses and structures of clusters V(W,Mo)/S/Cu(Ag) clusters, fourteen new V(Mo,W)/S/Cu(Ag) clusters being prepared and structurally characterized, of which eight are V/S/Cu clusters, three 3-D, five are 0-D, six are W(Mo)/S/Cu(Ag) clusters. The third-order nonlinear optic (MLO) properties of some compounds were investigated.Three V/S/Cu 3-D polymers have been synthesized by the reactions of [VS₄]^3- withCuSCN, CuCN, NH₄SCNand KCN in pyridine (py) or 4-methylpicolin. The reactions of [VS₄]^3- with CuCN, KCN in py or 4-methylpicolin resulted in two 3-D polymeric clusters, with the node was [VS₄Cu₆]³⁺ which connected by CN^-, the topological configuration were cube geometry. Only one topological configuration was found about the Mo(W)/S/Cu polymers that is diamond configuration, this is the first topological configuration about the V(Mo,W)/S/Cu polymers. The reactions of [VS₄]^3- with CuSCN, NH₄SCN in py resulted in one 3-D polymeric clusters, with two nodes were [VS₄Cu₆]³⁺ and Cu⁺ which were connected by SCN^-, the topological configuration were diamond geometry. But the node of the normal diamond geometry was only one constitution unit, in this polymer, the nodes were two constitution units, that is [VS₄Cu₆]³⁺ and Cu⁺. The structural pattern has not been observed in literatures.Five V/S/Cu clusters have been synthesized by the reactions of [VS₄]^3- with CuSCN, CuCN and CuI in py (or the ramifications such as 4-methylpicolin ). Those five clusters were isomers, the configurations were cage's icosahedrons, there is a S atom was substituted by a O atom in [VS₄]^3-, the cluster configurations [V₂S₆O₂Cu₆] were form by the asymmetry unit [VS₃OCu₃]. The third nonlinear optical was studied of one cluster, the cluster has very strong nonlinear absorption and self-focus properties. This has not been observed in literatures.Some neutral Mo(W)/ S /Cu(Ag) clusters have been synthesized. The relationship between the NLO and the contractual was studied, too. The neutral clusters which have been synthesized by the reactions of [MOS₃]^2- (M = Mo,W) as the star materials have more better third NLO properties than that have been synthesized by the reactions of[MS₄]^2- (M=Mo, W) as the star materials. A "half-open" cubane-like cluster has been synthesized.Density function theory (DFT) studies on nonlinear optical properties of neutral MOS₃Py₅Cu₃X (M = Mo, W; X = F, Cl, Br, I) clusters. From the calculations, we can concluded that the static first hyperpolarizability (β_tot) depended on the electronic communication between the donor and the acceptor. Those clusters MOS₃Py₅Cu₃X (M = Mo, W; X = F, Cl, Br, I) may have potential applications in the development of NLO materials.