W(Mo)/S/Cu Cluster-Organic Frameworks:Synthesis And Optical Properties

W（Mo）/S/Cu cluster-organic frameworks are self-assembled from copper salts,organic ligands and thiotungstate/thiomolybdate.These compounds have complex and varied structure types and potential applications in third-order nonlinear optics,adsorption and sensing,etc.In this thesis,seven novel W（Mo）/S/Cu cluster-organic frameworks were synthesized by solvent diffusion method,including one two-dimensional and six three-dimensional structures.In addition,three novel W/S/Cu cluster compounds were synthesized,including one zero-dimensional and two one-dimensional structures,namely:（1）{[WS₄Cu₃Cl（TPB）]·DMF}_n（2）[WS₄Cu₄I₂（TPB）]_n （3）[WS₄Cu₄（SCN）₂（TPB）]_n （4）{[WOS₃Cu₃]₂（SCN）₂（TPB）₃}_n（5）[WS₄Cu₄（CN）₂（TPB）]_n （6）[MoS₄Cu₄（CN）₂（TPB）]_n （7）{[NH₄][WS₄Cu₄（TPB）][Cu₂（CN）₅]}_n（8）{[WS₄Cu₃I（SCN）₂][Ni（Pytpy）₂]}_n （9）{[W₂O₂S₆Cu₄I₂][Ni（Pytpy）₂]}_n（10）{[WS₄Cu₃I（2-abpt）₂]·2-abpt} TPB=1,2,4,5-tetrakis（4-Pyridyl）benzene;DMF=N,N’-dimethylformamide;Pytpy=4′-（4-Pyridinyl）-2,2′:6′,2”-terpyridine;2-abpt=4-amino-3,5-bis（2-pyridyl）-1,2,4-triazole.Moreover,the optical properties（third-order nonlinear optics and luminescence detection）of some materials have been studied,which can be divided into four parts.1.Four novel W/S/Cu cluster-organic frameworks 1-4 were firstly synthesized by solvent diffusion method using the tetradentate ligand TPB and CuL（L=Cl,I,SCN）containing different anions.1 shows 2D network structure constructed by T-shaped[WS₄Cu₃]⁺cluster core and TPB ligand,and the topological symbol is（4⁴.6²）.2,3 have the same structure,both of which are 3D frameworks constructed by pentanuclear[WS₄Cu₄]²⁺cluster core,anion ligand and TPB ligand,and the topological symbol is（4⁴.6²）(4¹⁴.6¹⁴).4 shows 3D framework constructed by nest-shaped[WOS₃Cu₃]⁺cluster core with the topological symbol of（4³.6.8⁶）₂（4².8⁴）（4².6）₂.In the Z-scan test,2 has excellent third-order nonlinear optical absorption and refraction properties,1 and 3 have excellent third-order nonlinear optical absorption properties.2.Based on CN^–and TPB ligand,three novel W（Mo）/S/Cu cluster-organic frameworks5-7 were obtained by changing the synthesis conditions.In 5,each[WS₄Cu₄]²⁺cluster act as an 8-connected node and each TPB ligand act as a 4-connected node,forming binodal（4,8）-connected topology sturucture,and the topological symbol is（3².4².5²）(3⁴.4⁶.5¹².6⁶).6shows a similar structure to 2,except that the cluster core in 6 is[Mo S₄Cu₄]²⁺.In 7,each[WS₄Cu₄]²⁺cluster act as an 8-connected node,the[Cu₂（CN）₅]^3-anion unit and TPB ligand act as 4-connected nodes,forming trinodal（4,4,8）-connected topology sturucture,and the topological symbol is（4⁴.6²）₂(4¹⁴.6¹⁴).In the Z-scan test,6 shows no obvious NLO response,while 5 and 7 have excellent third-order nonlinear optical absorption and refraction properties.3.Two novel W/S/Cu cluster-metal polymers 8-9 were synthesized by introducing the transition metal Ni and the chelating ligand Pytpy.Both 8-9 are one-dimensional zigzag chain structures.The difference is that the cluster core in 8 is T-shaped cluster[WS₄Cu₃]⁺,while the cluster core in 9 is the first dimerized hexanuclear cluster[W₂O₂S₆Cu₄].In the luminescence detection experiment,9 displays highly sensitivity and selectivity for the detection of TNP.4.Based on the polydentate ligands 2-abpt,one novel W/S/Cu cluster compound 10 was synthesized.In 10,each T-shaped[WS₄Cu₃]⁺cluster bonds to two chelating ligands 2-abpt,forming a discrete W/S/Cu cluster.10 displays good water stability,and high sensitivity and selectivity for the detection of TNP.This represents the first example of discrete W/S/Cu cluster-based TNP sensor in aqueous medium.