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Humidity Sensitive Structural Dynamics and Solvatomagnetic Effects in a 3D Co(II)-Based Coordination Polymer
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00235
Long-Fei Wang 1 , Jiang-Zhen Qiu 1 , Si-Guo Wu 1 , Yan-Cong Chen 1 , Cui-Jin Li 2 , Quan-Wen Li 1 , Jun-Liang Liu 1 , Ming-Liang Tong 1
Affiliation  

A chiral Co(II)-based coordination polymer, [Co3(pimda)2(H2O)5] (1, H3pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) with 3D hyperkagomé topology is reported. Upon heating/cooling, the water molecules which are coordinated to a pair of crystallographically symmetric Co(II) ions are removed/recovered discretely in two steps, giving [Co3(pimda)2(H2O)4] (2) and [Co3(pimda)2(H2O)3] (3), which is evidenced by the reversible single-crystal-to-single-crystal (SCSC) structural transformations. As the coordination geometry of the two Co(II) ions changes from octahedron to trigonal bipyramid, obvious color change from pink for 1 to dark violet for 2 and 3 is observed. Further magnetic measurements demonstrate the presence of a solvatomagnetic effect from paramagnets for 1 and 2 to weak ferromagnet for 3. Moreover, as revealed by the variable-temperature crystallographic measurements, the first and second dehydration temperatures could be controlled from 298 K (25 °C) and 383 K (110 °C) sealed in a capillary (high humidity) to 255 K (−18 °C) and 307 K (34 °C) in dry N2 (low humidity), indicating the strong humidity sensitivity of the structural dynamics.

中文翻译:

基于3D Co(II)的配位聚合物中的湿度敏感结构动力学和溶剂磁效应

一种基于手性Co(II)的配位聚合物,[Co 3(pimda)2(H 2 O)5 ](1,H 3 pimda = 2-丙基-1H-咪唑-4,5-二羧酸)与3D超高聚物拓扑已报告。加热/冷却后,分两步分离/回收与一对晶体对称的Co(II)离子配位的水分子,得到[Co 3(pimda)2(H 2 O)4 ](2)和[Co 3(π)2(H 2 O)3 ](3),这由可逆的单晶到单晶(SCSC)结构转换证明。当两个Co(II)离子的配位几何形状从八面体变为三角双锥体时,观察到明显的颜色变化,从1的粉红色变为23的暗紫色。进一步的磁测量结果表明,从12的顺磁体到3的弱铁磁体都存在溶剂磁效应。此外,如通过可变温度晶体学测量所揭示的,可以将第一和第二脱水温度从密封在毛细管(高湿度)中的298 K(25°C)和383 K(110°C)控制到255 K(- 18°C)和307 K(34°C)在干燥N中2(低湿度),表示强烈的湿度敏感性结构动力学。
更新日期:2018-03-19
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