| The dissertation focuses on the syntheses,crystal structures,and luminescent properties of W/S/Ag cluster polymers and copper coordination polymers which were generated from heterocyclic unsymmetrical and flexible nitrogenous ligands.Thirteen new coordination polymers and cluster polymers have been synthesized and characterized,of which four are one-dimensional(1D)coordination polymers,five are two-dimensional(2D)coordination polymers,two are three-dimensional(3D)coordination polymers,and two 1D W/S/Ag cluster polymers.They are as follows:1[(CuI)(L1)]n(L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole)2[(CuBr)(L1)]n3[(CuCl2)(C6H7N)2(L1)]n4[(CuSCN)(L1)]n5[(CuCN)(L1)]n6{[CuN(CN)2](L1)}n7{(CuSCN)2[Cu(SCN)2]2(L1)3(DMF)2}n8[(CuSCN)(bpmp)]n(bpmp = N,N'-bis-(4-pyridylmethyl)piperazine)9[(CuSCN)(bpmp)]n10[(Cu4l4)(bpmp)3]n11[(Cu2I2)(bpmp)2]n12 {[Ni(4-pytpy)2][Ag2(SCN)4]}n13 {[Ni(4-pytpy)2][Ag2(N(CN)2)3(N03)DMSO]}n(DMSO = dimethyl sulfoxide)14 {[Ni(4-pytpy)2]2[Cu4(N(CN)2)7](NO3)(DMF)(DMSO)(H2O)4}n15 {[Co(4-pytpy)(N(CN)2)]2[Cu2(N(CN)2)4]}n16 {[Dy(NO3)2(HMP)4][WS4Ag]}n(HMP = Hexamethyl phosphoric triamide)17 {[Ce(NO3)2(HMP)4][WS4Ag]}n1.The coordination chemistry of the L1(L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole)with inorganic copper(?)halogen salts has been investigated.Three novel 1D coordination polymers,[(CuI)(L1)]n(1),[(CuBr)(L1)]n(2),and[(CuCl2)(C6H7N)2(L1)]n(3)were synthesized.The single crystal structures and luminescent properties were investigated in the solid state.2.The coordination chemistry of the L1 with inorganic copper(?)halogenoid salts has been investigated.Three novel 2D coordination polymers,[(CuSCN)(L1)]n(4),[(CuCN)(Ll)]n(5),and {[CuN(CN)2](L1)}n(6),were synthesized.The single crystal structures and luminescent properties were investigated in the solid state.3.The coordination chemistry of the L1 with inorganic mixed-valence copper(?,?)salts has been investigated.One novel 2D mixed-valence copper(?,?)coordination polymers,{(CuSCN)2[Cu(SCN)2]2(L1)3(DMF)2}n(7)was synthesized.The single crystal structures,thermal stability and luminescent properties were investigated in the solid state.4.The coordination chemistry of bpmp(bpmp = N,N'-bis-(4-pyridylmethyl)piperazine)ligand with cuprous thiocyanate has been investigated.Two copper(?)pseudohalides coordination polymers[(CuSCN)(bpmp)]n(8)and[(CuSCN)(bpmp)]n(9)have been designed and synthesized.Compounds 8 is an infinite single-walled coordination nanotube,while compound 9 have a 2D wave plan structure.We compered their synthesis,structure,solid-state luminescent and the possible reasons for leading the difference of structures between 8 and 9.5.The coordination chemistry of bpmp ligand with cuprous iodide has been investigated.Two coordination polymers[(Cu4I4)(bpmp)3]n(10)and[(Cu2I2)(bpmp)2]n(11)were synthesized.The two compounds constructed from[Cu4I4]-or[Cu2I2]-cores with bpmp exhibit different novel 2D layer structures.We discussed the synthesis,structure,solid-state luminescent and the possible reasons for leading the difference of structures between 10 and 11.6.Three novel 1D long chain heterobimetallic coordination polymers 12,13,14 and one novel 2D network coordination polymer 15 were obtained from the reaction of the precursors[M(4-pytpy)2](NO3)2(M = Ni,Co)and Cu+ or Ag+ with ancillary ligands([N(CN)2]-,[SCN]-).Single-crystal structures,thermal stabilities and fluorescence properties of these compounds have been investigated.7.Study on the syntheses and crystal structures of the rare earth cations inducing 1D W/S/Ag cluster polymers:The reactions of[NH4]2[WS4]with Ag+ induced by Dy3+ and Ce3+ coordinated with HMP(HMP = Hexamethyl phosphoric triamide)solvent as templates led to the formation of two 1D helical chain and linear W/S/Ag cluster polymers. |
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