Synthesis,Characterization And Properties Of Olefin-Cu(â… )coordination Polymers Based On N-heterocyclic Compounds

In recent years,in the field of organometallic chemistry and coordination chemistry,researchers are keen to polymer self-assembly and molecular construction,especially attractive olefin-copper（Ⅰ）complexes with nitrogen heterocyclic compounds.Diversification of olefin-copper（Ⅰ）complexes based on nitrogen heterocyclic ring has a multifunctional applications,such as fluorescence,ferroelectric,dielectric,phase change,chiral separation,olefin purification,bionics and catalysis of organic reactions.On the basis of investigating vast amount of literature,we present here the synthesis,crystal structure and spectroscopy of a series of olefin-Cu（Ⅰ）complexes with homopiperazine,morphine and 2,5-dimethyl piperazine as flexible ligands containing olefin functional group.Under solvothermal or hydrothermal reaction conditions,seven single crystals,including five olefin-Cu（Ⅰ）complexes and two metal-organic compounds,have been synthesized and characterized.Some of its physical properties,such as dielectric constant and luminescent property are given in this dissertation.1.Olefin-Cu（Ⅰ）complexes based on N-heterocyclic compounds as flexible ligands 1.1.Olefin-Cu（Ⅰ）complexes with homopiperazine derivatives as building blocks,two coordination polymers are obtained C11H19N2Br₂Cu2（1）and C23H28N2CuBr·CH4O（2）Olefin-Cu（Ⅰ）complex 1 and 2 was prepared from the ligands,1,4-diallyl-1,4-diazepane and 1,4-bis（4-vinylbenzyl）-1,4-diazepane,based on homopiperazine and CuBr under solvothermal reaction condition,respectively.In the compounds 1 and 2,Cu centers were coordinated with two N and one C=C from ligands forming 1D chain structures.Dielectric constants of compound 1 and 2 changes with the temperature and the frequency.In addition,the fluorescence test showed that the complexes 1 and 2 in solid state stimulated to produce blue light,which can be used as potential fluorescent materials.1.2.Olefin-Cu（Ⅰ）complex with morphine derivative as building block,C₁₃H₁₄NOCuCl（3）Olefin-Cu（Ⅰ）complex 3 was prepared from the ligand,4-（4-vinylbenzyl）morpholine,based on morphine and CuCl under solvothermal reaction condition.In compound 3,Cu centers were coordinated with two N and one C=C from ligands forming 1D chain structures.Dielectric constants of 3 keeps stable on the test temperature and the frequency.What’s more,the fluorescence property showed that 3 in solid state stimulated to produce blue light,which can be used as potential fluorescent materials.1.3.Olefin-Cu（Ⅰ）complexes with 2,5-dimethyl piperazine derivatives as building blocks,two coordination polymers are obtained C12H15NCu3Cl4（4）and C₁₂H₁₅NCu₃Br₄（5）Olefin-Cu（Ⅰ）complex 4 and 5 was prepared by 2,5-dimethyl-1,4-bis（4-vinylbenzyl）piperazine and CuCl,2,5-dimethyl piperazine and CuBr under solvothermal reaction conditions,respectively.In compound 4 and 5,Cu centers were coordinated with two N and one C=C from ligands forming 1D chain structures.Dielectric constants of Complex 4 and complex 5 keeps stable on the test temperature and the frequency.In addition,the fluorescence test showed that complex 4 and 5 in solid state stimulated to produce yellow warm color,which can be used as potential fluorescent materials.2.Metal-organic compound by self-assembly of homopiperazine and transition metal.2.1.Metal-organic compound based on homopiperazine with CuBr[Cd（hpip）Br₂]n（6）The crystal structure of 6 was determined by X-ray diffraction analysis,which forming 3D network structure.Dielectric constant of 6 changes with the temperature and frequency,which is higher than other similar compounds.2.2.Metal-organic compound based on homopiperazine with CuCl（hpip）₂Cu₈Cl₁₀（7）The crystal structure of 7 was determined by X-ray diffraction analysis,which forming 2D Cu（I/II）mixed-valence structure.Dielectric constants of 7 changes with the temperature and frequency.