Synthesis,structures, And Optical Properties Of Supramolecular Compound Based On Nitrogen Heterocyclic Dithioether Ligands And Divalent Cations Template

Now in the field of supramolecular chemistry,what attracts scientists’ attention is not only the novel structures of supramolecular polymers,but the special functions as well.There are a wide variety of nitrogen heterocyclic organic ligands and organic cations that can react with Cu/Ag halide/pseudohalide to synthesize a series of supramolecular polymers with novel structures and special optical,electrical,magnetic,catalytic performance and semiconductive functions.In this thesis,we have synthesized 4 nitrogen heterocyclic flexible multi-topic dithioether ligands containing similar structure with different length of alkyl chain and two nitrogen-containing heterocyclic divalent cations,and obtained ten functional supramolecular polymers by reacting with Cu/Ag halide/pseudohalide.In addition,we analyzed the structures and properties of compounds 1-10 by a variety of characterization techniques.First,basing on 4-mercaptopyridine,we synthesized four nitrogen heterocyclic flexible multi-topic dithioether ligands containing similar structure with different length of alkyl chain,and by reacting with Cu/Ag halide/pseudohalide we obtained compounds 1-7: {[Bpytm]CuI}n（1）,{[Bpyte]（CuI₂）₂}_n（2）,{[Bpytp]CuI₂}_n（3）,{[Bpytp₃（CuBr₂）₃}n（4）,{[Bpytp]Cu（SCN）₂（CH₃CN）}_n（5）,{[Bpytb]Cu（SCN）₂（DMF）}_n（6）,{[Bpytb]Ag₂I₃}_n（7）,（Bpytm = 1,1-bis（4-pyridylthio）methylene,Bpyte = 1,2-bis（4-pyridylthio）ethane,Bpytp = 1,3-bis（4-pyridylthio）propane,Bpytb = 1,4-bis（4-pyridylthio）butane）.We analyzed the compositions of compounds 1-7 by XRD,IR,SEM-EDS and EA.Besides,we characterized the properties of compounds 1-7 by fluorescence spectrum,ultraviolet-visible absorption spectrum and thermogravimetric analysis.The results showed that compounds 1-3 had a 2D network structure,and compounds 4-7 had a 1D chain structure.Compound 1 could act as a fluorescent sensor for the effective detection of Fe3+.Compounds 3-7 demonstrated good photocatalytic abilities for methyl orange（MO）irradiated by visible light.Then we employed 1-2-（Pyridinium-1-yl）-1-ethenyl] pyridinium dibromide and 1,3-bis（4-cyanopyridine）propane dibromide as bivalent cations template to reacting with CuSCN and CuBr,and obtained compounds 8-10: {（Pepy）[Cu₂（SCN）₄]}_n（8）,{（Pepy）[Cu₂Br₄]}_n（9）,{（Bcpyp）[Cu₂（SCN）₄]}_n（10）.The results indicated that compound 8 showed a 2D polypseudorotaxane structure,compound 9 showed a 1D chain structure,and compound 10 showed a 3D polypseudorotaxane structure.Compounds 9-10 demonstrated good photocatalytic abilities for methyl orange（MO）irradiated by visible light,besides,compound 10 showed remarkable photocatalytic abilities for rhodamine B（RhB）or methylene blue（MB）.