吡啶基苯修饰的氮氧自由基-Mn^(II)-Ln^(III)四核簇的合成、晶体结构、发光及磁性能研究  

Synthesis,Crystal Structure,Luminescent and Magnetic Properties of Pyridyl Phenyl Substituted Nitronyl Nitroxide Radical-Mn^(II)-Ln^(III)Tetranuclear Clusters

作　　者：李宝毅 何敏[2] 李弘道 LI Baoyi;HE Min;LI Hongdao(Department of Chemistry and Chemical Engineering,Taiyuan Institute of Technology,Taiyuan 030008,China;School of Chemistry and Chemical Engineering,North University of China,Taiyuan 030051,China)

机构地区：[1]太原工业学院化学与化工系,太原030008 [2]中北大学化学化工学院,太原030051

出　　处：《人工晶体学报》2024年第10期1769-1775,共7页Journal of Synthetic Crystals

基　　金：太原工业学院科研启动基金(2022LJ014);山西省基础研究计划项目(20210302124460)。

摘　　要：本文通过5-(4-吡啶基)苯基修饰的氮氧双自由基与铽/钬离子、锰离子反应,构建了两例同构的氮氧双自由基-稀土-过渡异自旋簇[Ln_(2)Mn_(2)(hfac)_(10)(NITPhPybis)_(2)][Ln=Tb 1,Ho 2]。在该体系中,两个双自由基配体NITPhPybis凭借两个吡啶环上的氮原子和两个氮氧基团同两个Mn(II)离子结合。与此同时,每个双自由基配体NITPhPybis凭借两个相邻的N-O基团封装一个Ln(III)离子,最终构成了一个中心对称的类环形异金属四核簇。此外,本文还对配合物的直流、交流磁性和荧光性质进行了分析研究。磁动力学研究结果显示多核簇1-TbMn展现慢磁弛豫行为;荧光性能测试结果表明多核簇1-TbMn和2-HoMn表现出铽或钬离子的特征荧光。5-(4-pyridyl)phenyl substituted functionalized nitronyl nitroxide biradical ligand holds Mn II ions and Tb III/Ho III ions together to yield 3d-4f-biradical heterospin clusters,namely,[Ln_(2)Mn_(2)(hfac)_(10)(NITPhPybis)_(2)][Ln=Tb 1,Ho 2],wherein,two NITPhPybis radicals ligate two Mn II ions via two NO groups and two nitrogen-atoms from pyridine rings.At the same time,each NITPhPybis encapsulates one Ln III ion through chelating mode with adjacent NO groups,generating an annular centrosymmetric heterometallic tetranuclear system.In addition,the direct current and alternating current magnetic properties and luminescent behavior were systematically studied.Magnetodynamic studies uncover that the cluster 1-TbMn exhibits slow magnetic relaxation.The fluorescence of two polynuclear clusters show the characteristic fluorescence of Tb III or Ho III ions.

关 键 词：氮氧双自由基 异自旋配合物 镧 过渡金属 自组装 配位反应 

分 类 号：O641.4[理学—物理化学]