Redox Activities of Metal–Organic Frameworks Incorporating Rare-Earth Metal Chains and Tetrathiafulvalene Linkers,Inorganic Chemistry

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Redox Activities of Metal–Organic Frameworks Incorporating Rare-Earth Metal Chains and Tetrathiafulvalene Linkers
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-03-04 00:00:00 , DOI: 10.1021/acs.inorgchem.8b03299
Jian Su ₁ , Tian-Hao Hu ₁ , Ryuichi Murase ₂ , Hai-Ying Wang ₁ , Deanna M. D’Alessandro ₂ , Mohamedally Kurmoo ₃ , Jing-Lin Zuo ₁

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Metal–organic frameworks (MOFs) incorporating lanthanide nodes and tetrathiafulvalene (TTF) linkers offer a viable approach for combining redox activity and magnetism in one material. Four rare-earth lanthanide ions (RE = Tb, Dy, Ho, and Er) were found to form isostructural MOFs consisting of metal chains bridged by redox-active tetrathiafulvalene-tetrabenzoate (TTFTB^4–) whereby the carboxylate moieties act in both anti-anti and syn-syn coordination modes. These materials display tunable redox-active properties and slow magnetic relaxation phenomenon (Er and Dy). While the as-synthesized crystals contain the neutral diamagnetic TTF moiety, using either a solid-solution electrochemical method or iodine oxidation transforms part of the latter to the paramagnetic TTF^•+ radical in a single-crystal-to-single-crystal manner without altering the internal structure of the building chains and the frameworks. This is accompanied by inclusion of I₃^– replacing some of the solvents, as well as changes in the central C–C bond length of TTFTB, a strong EPR response at g ∼ 2, and an enhancement of the reflectance at low energies originating from absorption by the radical.

中文翻译：

结合稀土金属链和四硫富瓦烯键的金属有机骨架的氧化还原活性

包含镧系元素节点和四硫富瓦烯（TTF）接头的金属有机框架（MOF）提供了一种在一种材料中结合氧化还原活性和磁性的可行方法。四稀土镧系元素离子（RE = Tb时，镝，钬，和Er）被发现，以形成同构的MOF自由金属链桥接由氧化还原活性硫富瓦烯-四苯甲酸（TTFTB ^4-），由此羧酸盐部分在这两个作用的抗-防和SYN - SYN协调模式。这些材料显示出可调节的氧化还原活性和缓慢的磁弛豫现象（Er和Dy）。合成后的晶体包含中性的反磁性TTF部分时，使用固溶电化学方法或碘氧化法，可以将其一部分以单晶至单晶的方式转变为顺磁性TTF ^•+自由基，而无需改变建筑链的内部结构和框架。这伴随着通过包含第I ₃^-代替一些溶剂，以及改变在TTFTB，在强EPR响应的中心C-C键长克〜2，在从低能量始发的反射率的增强被自由基吸收。

更新日期：2019-03-04

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