基于席夫碱配体构筑的Ln_(2)^(Ⅲ)配合物的结构、荧光性质及生物活性  

Crystal structure, fluorescence properties, and biological activity of Ln_(2)^(Ⅲ) complexes based on Schiff base ligand

作　　者：辛晓艳 陈凤姣 李文钰 王捷 杨晨 李敏[2] 石瑛[2] 王文敏 XIN Xiao-Yan;CHEN Feng-Jiao;LI Wen-Yu;WANG Jie;YANG Chen;LI Min;SHI Ying;WANG Wen-Min(College of Chemistry and Materials,Taiyuan Normal University,Jinzhong,Shanxi 030619,China;Institute for Carbon Neutrality,Taiyuan Normal University,Jinzhong,Shanxi 030619,China)

机构地区：[1]太原师范学院化学与材料学院,晋中030619 [2]太原师范学院碳中和研究院,晋中030619

出　　处：《无机化学学报》2023年第1期1-12,共12页Chinese Journal of Inorganic Chemistry

基　　金：山西省高校科技创新项目(No.2021L404)资助。

摘　　要：以多齿席夫碱配体H_(2)L(H_(2)L=(E)-N′-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体,与Ln(acac)_(3)·2H_(2)O(Ln=Tb、Ho、Er;acac-=乙酰丙酮根)反应,通过溶剂热法,成功得到了3例新的双核稀土配合物[Ln_(2)(acac)_(2)(L)_(2)(C_(2)H_(5)OH)_(2)](Ln=Tb(1)、Ho(2)、Er(3))。单晶X射线衍射分析表明:配合物1~3的结构主要由2个Ln^(Ⅲ)离子、2个乙酰丙酮根(acac^(-))、2个L^(2-)及2个C_(2)H_(5)OH组成,中心Ln^(Ⅲ)离子通过2个μ_(2)-O原子相互连接,形成一个平行四边形的Ln_(2)O_(2)核心。固体荧光实验测试结果表明:配合物1在室温下表现出TbⅢ离子的荧光特征发射峰。此外,生物活性研究表明,与配体H_(2)L和稀土离子相比较,配合物1~3具有更强的抗菌活性。采用紫外光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了配合物1~3与小牛胸腺DNA之间的相互作用,结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。Three new binuclear Ln-based complexes with the formula[Ln_(2)(acac)2(L)2(C_(2)H_(5)OH)_(2)](Ln=Tb(1),Ho(2),Er(3);acac-=acetylacetonate) have been synthesized via the solvothermal method by using a polydentate Schiff base ligand(H_(2)L=(E)-N′-(3-ethoxy-2-hydroxyb enzylidene)-3-hydroxypicolinohydrazide) reacting with Ln(acac)_(3)·2H_(2)O.Single-crystal X-ray structures reveal that complexes 1-3 are mainly composed of two Ln^(Ⅲ)ions,two acac-ions,two L^(2-)ions,two C_(2)H_(5)OH molecules,and the two central Ln^(Ⅲ)ions are connected by two μ_(2)-O atoms forming a “parallelogram-shaped” Ln_(2)O_(2)core.The solid-state fluorescence property shows that the emission spectrum of complex 1 exhibited the characteristic emissions of TbⅢions under the excitation of 296 nm.For complex 1,four characteristic emission peaks were observed at 490,545,585,and 620 nm,corresponding to the transitions of Tb^(Ⅲ)ion from ~^(5)D4to ~^(7)FJ(J=6,5,4,3).In addition,the biological activity study shows that complexes 1-3 had stronger antibacterial activity than H_(2)L and Ln(acac)_(3)·2H_(2)O.The interaction between complexes 1-3 and DNA was studied by ultraviolet spectroscopy,cyclic voltammetry,gel electrophoresis,and fluorescence spectroscopy.The results reveal that complexes 1-3 could bind to calf thymus DNA mainly by intercalation.CCDC:2183865,1;2183867,2;2183869,3.

关 键 词：Ln_(2)配合物 晶体结构 荧光性质 生物活性 DNA作用 

分 类 号：O614.341[理学—无机化学] O614.343[理学—化学] O614.344