吡啶基苯修饰的氮氧自由基-MnII-LnIII四核簇的合成、晶体结构、发光及磁性能研究

人工晶体学报 ›› 2024, Vol. 53 ›› Issue (10): 1769-1775.

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

李宝毅¹, 何敏², 李弘道¹

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

收稿日期:2024-05-28 出版日期:2024-10-15 发布日期:2024-10-21
通信作者: 李弘道,博士,副教授。E-mail:lihong.dao@163.com
作者简介:李宝毅(1983—),男,山东省人,博士,高级工程师。E-mail:109052158@qq.com
基金资助:
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)

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

LI Baoyi¹, HE Min², LI Hongdao¹

1. Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China;
2. School of Chemistry and Chemical Engineering, North University of China, Taiyuan 030051, China

Received:2024-05-28 Online:2024-10-15 Published:2024-10-21

摘要/Abstract

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[Ln₂Mn₂(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。

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

Abstract: 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, [Ln₂Mn₂(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.

Key words: nitronyl nitroxide biradical, heterospin complex, lanthanide, transition metal, self-assembly, coordination reaction

中图分类号:

O641.4

李宝毅, 何敏, 李弘道. 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[J]. 人工晶体学报, 2024, 53(10): 1769-1775.

LI Baoyi, HE Min, LI Hongdao. Synthesis, Crystal Structure, Luminescent and Magnetic Properties of Pyridyl Phenyl Substituted Nitronyl Nitroxide Radical-Mn^II-Ln^III Tetranuclear Clusters[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(10): 1769-1775.

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