A series of lanthanide(III) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence properties
A series of lanthanide(III) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence properties
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一系列源自吡啶二羧酸酯配体的镧系元素（III）金属有机骨架：单分子磁体行为和发光特性
DOI：
10.1039/d0dt02736g
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发表时间：
2020
影响因子：
4
通讯作者：
Liu Xiangyu
中科院分区：
文献类型：
--
作者：
Zhang Chengcheng;Ma Xiufang;Cen Peipei;Jin Xiaoyong;Yang Jinhui;Zhang Yi-Quan;Ferr;o-Soria Jesus;Pardo Emilio;Liu Xiangyu
LnIII离子与多功能吡啶基修饰的二羧酸配体反应，形成了一系列新型三维（3D）Ln-MOFs，[Ln 3（pta）4（Hpta）（H2O）]·xH 2 O（Ln = Dy（1），Eu（2），Gd（3），Tb（4），H2 pta = 2-（4-吡啶基）-对苯二甲酸，对于1，x = 6，对于2，x = 2.5，对于3，x = 1.5，对于4，x = 2）。Ln 3+离子作为九配位的松饼球，相互连接以产生三核{Ln 3（OOC）6 N2} SBU，其进一步扩展为有趣的3D拓扑结构。据我们所知，Dy-MOF表现出零场单分子磁体（SMM）行为，在先前报道的基于3D MOF的Dy-SMM中具有最大的有效能垒。对稀释样品（1@Y）的分析和从头计算结果表明，热辅助慢弛豫主要是由单离子磁性引起的.此外，荧光测量表明，H2 pta可以敏化EuIII和TbIII的特征发光。
The reactions of LnIII ions with a versatile pyridyl-decorated dicarboxylic acid ligand lead to the formation of a series of novel three-dimensional (3D) Ln-MOFs, [Ln3(pta)4(Hpta)(H2O)]·xH2O (Ln = Dy (1), Eu (2), Gd (3), Tb (4), H2pta = 2-(4-pyridyl)-terephthalic acid, x = 6 for 1, 2.5 for 2, 1.5 for 3 and 2 for 4). The Ln3+ ions act as nine-coordinated muffin spheres, linking to each other to generate trinuclear {Ln3(OOC)6N2} SBUs, which are further extended to be interesting 3D topological architectures. To the best of our knowledge, the Dy-MOF exhibits zero-field single-molecule magnet (SMM) behaviour with the largest effective energy barrier among the previously reported 3D MOF-based Dy-SMMs. The combined analyses of a diluted sample (1@Y) and ab initio calculations demonstrate that the thermally assisted slow relaxation is mainly attributed to the single-ion magnetism. Furthermore, fluorescence measurements reveal that H2pta can sensitize EuIII and TbIII characteristic luminescence.