五个吡嗪缩氨基硫脲过渡金属配合物的合成、结构和荧光性质（英文）  

Crystal Structures and Fluorescence Properties of Five Transition Metal Complexes with Pyrazine Thiosemicarbazone

作　　者：高亮亮 黄山秀 康瑞芳 代耿耿 吴伟娜 王元 陈忠 GAO Liang-Liang;HUANG Shan-Xiu;KANG Rui-Fang;DAI Geng-Geng;WU Wei-Na;WANG Yuan;CHEN Zhong(College of Chemistry and Chemical Engineering, Henan Key Laboratory of Coal Green Conversion, Henan Polytechnic University, Jiaozuo, Henan 454000, China;School of Materials and Mechanical and Electrical Engineering, Jiangxi Science and Technology Normal University, Nanchang 330013, China)

机构地区：[1]河南理工大学化学化工学院河南省煤炭绿色转化重点实验室,焦作454000 [2]江西科技师范大学材料与机电学院,南昌330013

出　　处：《无机化学学报》2019年第5期901-909,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21001040);河南省自然科学基金(No.182300410183,162300410011);江西省自然科学基金(No.20181BAB206011);河南省教育厅高等学校重点科研基金(No.19A150001);江西省教育厅科学技术研究项目(No.GJJ170665);河南理工大学校内基金(No.T2018-3,J2015-4);江西科技师范大学校内基金(No.2015QNBJRC006)资助

摘　　要：合成并通过单晶衍射、元素分析及红外光谱表征了配合物[NiL_2](1),[Zn(HL)_2](NO_3)_2(2),[Cd(HL)_2](NO_3)_2(3),[Cu_2L_2(NO_3)_2](4)和[Cu_2(L)_2(SO_4)]·4CH_3OH (5)的结构(HL为2-乙酰-3-甲基吡嗪-缩N-乙基氨基硫脲)。单晶衍射结果表明,配合物1中,Ni(Ⅱ)离子中心与2个脱氢的缩氨基硫脲配体中的N_2S供体配位,形成扭曲的八面体配位构型。在配合物2和3中,中心Zn(Ⅱ)和Cd(Ⅱ)离子与配合物1中Ni(Ⅱ)离子配位构型相同,但缩氨基硫脲为三齿中性配体。而配合物4和5中均存在双核的Cu_2S_2中心,每个Cu(Ⅱ)均采取扭曲的四方锥配位构型,所不同的是外轴向配位点分别由单齿配位的硝酸根和μ_2-桥联的硫酸根所占据。此外,荧光光谱表明配合物1～5与DNA的相互作用强于配体。Five transition metal complexes,[NiL2](1),[Zn(HL)2](NO3)2 (2),[Cd(HL)2](NO3)2 (3),[Cu2L2(NO3)2](4) and [Cu2(L)2(SO4)]·4CH3OH (5) based on HL (HL=3-methyl-2-acetylpyrazine N(4)-ethylthiosemicarbazone) have been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that the Ni(Ⅱ) ion in complex 1 with a distorted octahedron geometry is surrounded by two neutral thiosemicarbazone(TSC) ligand with N2S donor set. On the contrary, the ligand TSC is deprotonated in the complexes 2 and 3, although the Zn(Ⅱ) and Cd(Ⅱ) ions possess similar coordination geometry as that of Ni(Ⅱ) in complex 1. The dimeric Cu2S2 cores are found in complexes 4 and 5, and each of the Cu(Ⅱ) adopted a distorted square pyramid coordination geometry. The outer axial sites are occupied by two monodentate NO3^- and a μ2-SO4^2- in complexes 4 and 5, respectively. In addition, the fluorescence spectra indicate that the interactions of complexes with DNA are stronger than that of ligand HL. CCDC: 1434105, HL;1434106, 1;1434107, 2;1434108, 3;1434109, 4;1434110, 5.

关 键 词：晶体结构 荧光 吡嗪 缩氨基硫脲 过渡金属配合物 

分 类 号：O614.913[理学—无机化学] O614.241[理学—化学]