Syntheses And Crystal Structure Of Copper(Ⅰ) And Silver(Ⅰ) Coordination Polymers Based On N-heterocyclic Ligands

In recent years,metal-organic coordination polymers containing[Cu（I）X（X=CN^-,SCN^-,Cl^-,Br^-,I^-）]or[Ag CN]substructural units have attracted great attentions,owing to their various crystal structures and potential applications in luminescence,conductor,magnetism,adsorbent and catalysis.N-heterocyclic ligands have several coordination atoms,which can provide a variety of coordination modes to form coordination polymers with different structures.In this thesis,the reactions of two types of N-heterocyclic ligands（triangular and flexible chain）with Cu（I）X（X=CN^-,I^-,Br^-,SCN^-）and Ag CN were studied by changing the N-heterocyclic ligands and reaction conditions.24 novel coordination polymers were synthesized and characterized by elemental analysis,infrared spectroscopy and powder X-ray diffraction.Their molecular and crystal structures were determined by single crystal X-ray diffraction.The fluorescence and thermal properties of several complexes were studied.The results were briefly described as follows.1.Eight 2D and 3D coordination polymers were prepared through four triangular N-heterocyclic ligands and Cu（I）X（X=CN^-,I^-,Br^-）substructural unit under hydrothermal conditions.The effects of reaction temperature,solvent and metal salt on the composition and crystal structure of the product were discussed.The eight complexes are[Cu₃（CN）₃（tib）]_n（1）、[Cu₂（CN）₂（tib）]_n（2）、isomers[Cu₄（CN）₄（tib）]_n（3）and[Cu₄（CN）₄（tib）]_n（4）、{[Cu₃（CN）₃（4-tpt）]·2（CH₃CN）}_n（5）、[Cu₂Br₂（3-tpt）]_n（6）、[Cu₄（CN）₄（Htpim）]_n（7）and[Cu₆I₆（Htpim）₂·2H₂O]_n（8）（tib=1,3,5-tris（1-imidazolyl）benzene,tpt=2,4,6-tripyridyl-1,3,5-triazine,Htpim=2,4,5-tris（4-pyridyl）-imidazole）.Complexes 1-4 were synthesized by the same ligand tib under different reaction conditions.Complexes 1,3 and 4 have 3D polymeric structures,and complex 2 is a 2D coordination polymer.The cyanide in the complex5 was derived from CH₃CN solvent molecule.Complex 7 is a 3D coordination polymer formed by Htpim and[Cu（CN）]_n chain.Complexes 6 and 8 are two 3D supramolecular polymers withπ-πstacking interaction and hydrogen bonds.2.Twelve Cu（I）and a Cu（II）coordination polymers were constructed by flexible-chain N-heterocyclic ligands under hydrothermal conditions:[Cu（CN）（bpmp）_0.5]_n（9）and its isomer[Cu（CN）（bpmp）_0.5]_n（10）、[Cu₇（CN）₇（bpmp）]_n（11）、[Cu₆（CN）₆（bpmp）₂]_n（12）、[Cu₃（CN）₃（bpmp）]_n（13）、[Cu₂I₂（bpmp）]_n（14）、[Cu₈（CN）₈（btmb）₂]_n（15）、[Cu₂（CN）₂（o-btmb）_0.5]_n（16）、[Cu Br₂（m-btmb）]_n（17）、[Cu₅（CN）₅（btmbp）]_n（18）、[Cu₂（CN）₂（bpe）_0.5]_n（19）、[Cu（CN）（azim）_0.5]_n（20）and[Cu₂（SCN）₂（bpp）]_n（21）（bpmp=1,4-bis（4-pyridylmethyl）piperazin,btmb=bis（1,2,4-triazole-1-ylmethyl）benzene,btmbp=bis（1,2,4-triazol-1-ylmethyl）biphenyl,bpe=1,2-bis（4-pyridyl）ethane,azim=azo-biimidazole benzene,bpp=1,3-bis（4-pyridyl）propane）.Complexes 9-13 were assembled by bpmp ligand and Cu CN unit in different reaction conditions.Complexes 9 and 10 have similar molecular formulas,but different connection modes of cyanide,which show 1D ladder-like and3D network structure,respectively.Complexes 11 and 13 are two 3D MOFs.Complex 12 is a 3D polymer with two different pore sizes.Complex 14 is a porous3D MOF formed by bpmp ligand and Cu I.Complexes 15,16 and 17 are three coordination polymers constructed by three bis-triazole-substituted xylene derivatives.The pores formed in the structure of p-btmb（15）are a little larger than o-btmb（16）.Complex 18 using para-substituted triazole has similar structure like 15.Complex 19 is a 3D MOF formed by bpe ligand and[Cu CN]_n chain with a pore size of 0.9167×0.9605 nm².Complex 20 is composed of a long chain azim ligand linked to the serrated chain of[Cu（CN）]_n,forming an interesting structure like the vein of leaves.Complex 21 is a 2D network formed by[Cu₂（SCN）₂]_n zigzag chain and bridging bpp ligand.3.Three coordination polymers containing[Ag（CN）]_n sub-structural unit were synthesized by different N-heterocyclic ligands under hydrothermal conditions:[Ag₂（CN）₂（tpt）]_n（22）,{[Ag（CN）（bpe）_0.5][Ag（CN）]}_n（23）and[Ag（CN）（btmb）_0.5]n（24）.The Ag-Ag metal bonds and Ag···Ag interaction（argentophilic interactions）play important roles in the structural construction of the three complexes.