Mo(W)/S/Cu Polymeric Clusters And [AgSCN]_n-based Coordination Polymers: Syntheses, Structures, Theoretical Calculations And Third-order Nonlinear Optical Properties

The dissertation focuses on the syntheses, crystal structures, theoretical calculations and third-order nonlinear optical (NLO) properties of the Mo(W)/S/Cu polymeric clusters and [AgSCN]n-based coordination polymers. Fourteen new Mo(W)/S/Cu polymeric clusters and three new [AgSCN]n-based coordination polymers have been synthesized and characterized, of which one is zero-dimensional (0-D) polymeric cluster, one is one-dimensional (1-D) polymeric cluster, twelve are three-dimensional (3-D) polymeric clusters, two are two-dimensional (2-D) coordination polymers and one is 3-D coordination polymer. They are as follows:1{[WS4Cu3(4,4'-pytz)3]·[N(CN)2]}n (4,4'-pytz=3,6-bis(4-pyridyl)tetrazine)2{(Et4N)[WS4Cu3(CN)2(4,4'-pytz)0.5]}n3{[WS4Cu4(CN)2(4,4'-pytz)2]·2DMF}n4{[WS4Ou4(CN)2(4,4'-pytz)2]·2DMF}n (3 and 4 are polymeric clusters isomers)5{[MoS4Cu4(CN)2(4,4'-pytz)2]·CH2C12-H2O}n6 [Ag(1,3-μ2-SCN)(μ2-hmt)]n (hmt=hexamethylenetetramine)7{[Ag(1,1,3-μ3-SCN)]2(μ2-hmt)}n8 [Ag(1,1,3-μ3-SCN)(μ4-hmt)0.5]n (7 and 8 are supermolecule isomers)9{[WS4Cu4Cl2(4,4'-pytz)3]·CH2Cl2}n10{[WS4Cu4Br2(4,4t-pytz)3]·2CH2Cl2}n11{[MoS4Cu4Br2(4,4'-pytz)3]·2CH2Cl2}n12{[WS4Cu4I2(4,4'-pytz)3]·2CH2Cl2}n13{[(MoS4Cu4)(NCS)4(4,4'-dpmh)2][(MoS4Cu4)(4,4'-dpmh)4-2H2O]}n (4,4'-dpmh=N,N'-bis(pyridin-4-ylmethylene)hydrazine)14{[WS4Cu4(CN)2(4,4'-dpmh)2]-2DMF}n15{(Me4N)3[(WS4)2Cu]-CH3CN}16{(Me4N)[MoS4Cu]}n17{(Et4N)[(MoS4Cu4(CN)3]}n1. Unconventional clusters had been applied in the synthesis of 3-D Mo(W)/S/Cu polymeric clusters. A novel 3-D W/S/Cu polymeric cluster 1 with a heavily distorted "ACS" topology was first constructed from the flywheel-shaped cluster [WS4Cu3]+. The construction of novel Mo(W)/S/Cu polymeric cluster with odd number connected modes had been explored. A novel 3-D the W/S/Cu polymeric cluster 2 had been first constructed by the use of the T-shaped cluster [WS4Cu3]+as unique 5-connected manner. The DFT calculation has afforded insight into the spectral characterization of 1 and 2.2. Solvent-induced methods had been studied for the generation of 3-D Mo(W)/S/Cu polymeric clusters and [AgSCN]n-based coordination polymer. A series of Mo(W)/S/Cu polymeric clusters have been first constructed by pentanuclear planar "open" cluster [Mo(W)S4Cu4]2+ as building units and bidentate bridging ligand 4,4'-pytz as the connector.3 and 4 are polymeric cluster isomers.4 and 5 contain the unprecedented arched distorted 4,4'-pytz bridges. Three [AgSCN]n-based coordination polymers had been synthesized by AgSCN and hmt ligands.7 and 8 are supramolecular isomers. Furthermore, their absorption spectra were explored.3. The interdiffusion procedure had been applied in the syntheses of 3-D Mo(W)/S/Cu polymeric clusters. A series of 3-D Mo(W)/S/Cu polymeric clusters were synthesized by cuprous halides, ammonium thiomolybdates(thiotungstates) and 4,4'-pytz bridge ligand.4. Two 3-D Mo(W)/S/Cu polymeric cluster were successfully constructed by pentanuclear planar "open" [Mo(W)S4Cu4]2+ building clusters in the presence of longer bridging ligand 4,4'-dpmh.5. The influence on the self-assembly of Mo(W)/S/Cu polymeric clusters had been studied by the molar weight of reactant. For the first time, the multifarious structures of Mo(W)/S/Cu polymeric clusters had been prepared by modulating the molar weight of melamine.