一例由多齿席夫碱构筑的Tb_(2)配合物的结构、荧光性质及生物活性  

A Tb_(2)complex based on polydentate Schiff base:Crystal structure,fluorescence properties,and biological activity

作　　者：马鑫 孙娅 孙楠 康倩 张佳佳 朱瑞涛[1] 高晓丽 MA Xin;SUN Ya;SUN Na;KANG Qian;ZHANG Jiajia;ZHU Ruitao;GAO Xiaoli(College of Chemistry and Materials,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

出　　处：《无机化学学报》2024年第7期1347-1356,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21671124);山西省自然科学基金(No.20210302123324)资助。

摘　　要：使用多齿希夫碱配体H_(4)L(H_(4)L(H_(4)L=N',N"-((1E,1'E)-(1,10-菲咯啉-2,9-二酰基)双(亚甲基)双(2-羟基苯甲酰肼))与Tb(acac)_(3)·2H_(2)O反应(acac^(-)=乙酰丙酮根),通过溶剂热法,设计并合成了一例结构新颖的双核铽配合物[Tb_(2)(L)(H_(2)L)]·2CH_(3)OH·CH_(3)CN(1),并研究了该配合物的结构、荧光性质及生物活性。单晶X射线衍射分析表明该配合物主要含有2个Tb^(Ⅲ)离子和2个失去不同质子的配体离子(L^(4)-和H_(2)L^(2-))。中心Tb1和Tb2离子都是九配位的,其几何构型呈现扭曲的呼啦圈形。固体荧光实验测试结果表明:该配合物在室温下表现出Tb^(Ⅲ)离子的荧光特征发射峰。生物活性研究表明,与配体H_(4)L和稀土离子相比较,配合物具有更强的抗菌活性。采用紫外可见光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了该配合物与小牛胸腺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。A new lanthanide binuclear Tb(Ⅲ)-based complex with the formula[Tb_(2)(L)(H_(2)L)]·2CH_(3)OH·CH_(3)CN(1)have been synthesized via the solvothermal method by using a polydentate Schiff base ligand(H_(4)L=N',N"-((1E,1'E)-(1,10-phenanthroline-2,9-diyl)bis(methaneylylidene))bis(2-hydroxybenzohydrazide))reacting with Tb(acac)_(3)·2H_(2)O(acac~-=acetylacetonate).It was characterized by IR,elemental analysis,single-crystal and powder X-ray diffraction.Single-crystal X-ray structure analysis reveals that complex 1 belongs to the triclinic system with P1 space group,and the asymmetric unit mainly includes two Tb~Ⅲions and two different deprotonated ligands(L^(4-)and H_(2)L^(2-)).Both centre Tb1 and Tb2 ions are nine-coordinated with a[N_(4)O_(5)]coordination environment.The coordination geometry is shown as a distorted hula-hoop.In addition,the biological activity study shows that the complex has stronger antibacterial activity than H_(4L)and Tb(acac)_(3)·2H_(2)O.The interaction between 1 and DNA was studied by UV-Vis spectroscopy,cyclic voltammetry,gel electrophoresis,and fluorescence spectroscopy.The results reveal that 1 could bind to calf thymus DNA mainly by intercalation.Ethidium bromide(EB)displacement experiments indicated that Stern-Volmer quenching constants of complexes 1 and H_(4L)were 1.04 and 0.30,respectively.CCDC:2293742.

关 键 词：Tb_(2)配合物 生物活性 DNA作用 荧光性质 晶体结构 

分 类 号：O614.341[理学—无机化学]