Syntheses And Crystal Structure Of Copper(?) And Silver(?) 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 with?-?stacking 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.