两例基于多齿二酰腙配体构筑的双核Gd配合物的晶体结构、磁热效应及生物活性  

Two dinuclear Gd(Ⅲ)‑based complexes constructed by a multidentate diacylhydrazone ligand:Crystal structure,magnetocaloric effect,and biological activity

作　　者：季甲[1] 郭朝阳 雷文妮 郑佳苇 秦浩容 闫嘉红 侯银玲[1] 辛晓艳 王文敏 JI Jia;GUO Zhaoyang;LEI Wenni;ZHENG Jiawei;QIN Haorong;YAN Jiahong;HOU Yinling;XIN Xiaoyan;WANG Wenmin(Key Laboratory of Preparation and Application of Micro&Mesoporous Nanomaterials of Guizhou Province,Kaili University,Kaili,Guizhou 556011,China;College of Chemistry and Materials,Taiyuan Normal University,Jinzhong,Shanxi 030619,China;Civil Aviation Modern Industry College,Ningxia Institute of Science and Technology,Shizuishan,Ningxia 753000,China)

机构地区：[1]凯里学院,贵州省微介孔纳米材料制备与应用特色重点实验室,凯里556011 [2]太原师范学院化学与材料学院,晋中030619 [3]宁夏理工学院民航现代产业学院,石嘴山753000

出　　处：《无机化学学报》2025年第4期761-772,共12页Chinese Journal of Inorganic Chemistry

基　　金：黔东南州科技计划项目(黔东南科合基础[2023]02号)资助。

摘　　要：利用大共轭二酰腙有机配体N',N‴-(1E,1'E)-(1,10-菲咯啉-2,9-二基)双(甲酰基乙基)双(2-羟基苯并肼)(H_(4)L)与Gd(NO_(3))3·6H_(2)O或Gd(dbm)3·2H_(2)O反应,得到了2例双核Gd_(2)配合物:[Gd_(2)(L)(H_(2)L)]·2CH_(3)OH·CH_(3)CN(1)和[Gd_(2)(H_(2)L)2(dbm)_(2)]·6CH_(3)CN(2)(Hdbm=二苯甲酰甲烷)。结构研究表明,Gd_(2)配合物1和2均属于三斜晶系,空间群为P1,然而它们的分子结构却不同,其中1显示蒲扇形状,而2为风车形状的笼子。磁性研究表明,2种Gd_(2)配合物表现出不同的磁致冷性能[-ΔS_(m)=23.35 J·kg^(-1)·K^(-1)(1)、15.09 J·kg^(-1)·K^(-1)(2)]。此外,配体与Ln(Ⅲ)之间的协同作用使2种Gd_(2)配合物表现出优异的抗菌活性。当Gd_(2)配合物与DNA相互作用时,Gd_(2)配合物主要插入或切割DNA。Two new binuclear Gd_(2) complexes with the molecular formula[Gd_(2)(L)(H_(2)L)]·2CH_(3)OH·CH_(3)CN(1)and[Gd_(2)(H_(2)L)2(dbm)2]·6CH_(3)CN(2)(Hdbm=dibenzoylmethane)have been obtained by using a large conjugated diacylhy-drazone organic ligand N',N‴-(1E,1'E)-(1,10-phenanthroline-2,9-diyl)bis(methaneylylidene)bis(2-hydroxy-benzo-hydrazide)(H_(4)L)reacting with Gd(NO_(3))3·6H_(2)O or Gd(dbm)3·2H_(2)O.Structure studies reveal that Gd_(2) complexes 1 and 2 belong to a triclinic crystal system with space group P1.Nevertheless,they show different molecule struc-tures.1 displays a cattail leaf fan shape,while 2 displays a pinwheel-shaped cage.Magnetic properties researches suggest that the two Gd_(2) complexes displayed different magnetic refrigeration(-ΔS_(m)=23.35 and 15.09 J·kg^(-1)·K^(-1) for 1 and 2,respectively).In addition,the synergistic interaction between ligand and Ln(Ⅲ) ions,promotes the two Gd_(2) complexes showing excellent antibacterial activity.When the Gd_(2)complexes interact with DNA,the Gd_(2) complexes mainly insert or cut DNA.CCDC:2299957,1;2299958,2.

关 键 词：双核Gd2配合物 晶体结构 磁制冷 抑菌活性 DNA结合 

分 类 号：O614.339[理学—无机化学]