Kuzevanova Iryna S, Kucheriv Olesia I, Hiiuk Volodymyr M, Naumova Dina D, Shova Sergiu, Shylin Sergii I, Kotsyubynsky Volodymyr O, Rotaru Aurelian, Fritsky Igor O, Gural'skiy Il'ya A
Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska St. 64, Kyiv 01601, Ukraine.
Department of Inorganic Polymers, Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41-A, Iasi 700487, Romania.
Dalton Trans. 2021 Jul 6;50(26):9250-9258. doi: 10.1039/d1dt01544c.
Hofmann-like cyanometallic complexes represent one of the biggest and well-known classes of FeII spin-crossover compounds. In this paper, we report on the first FeII Hofmann clathrate analogues with unsubstituted 1,2,3-triazole, which exhibit temperature induced spin transition. Two new coordination polymers with the general formula [FeII(1,2,3-triazole)2MII(CN)4] (M = Pt, Pd) undergo abrupt hysteretic spin crossover in the range of 190-225 K as revealed by magnetic susceptibility measurements. Two compounds are isostructural and are built of infinite cyanometallic layers which are supported by 1,2,3-triazole ligands. The thermal hysteresis loop is very stable at different scan rates from 0.5 to 10 K min-1. The compounds display strong thermochromic effect, changing their colour from pink in the low-spin state to white in the high-spin state. Our findings show that 1,2,3-triazole is suitable for elaboration of spin-crossover Hofmann clathrate analogues, and its use instead of more classical azines can advantageously expand this family of complexes.
类霍夫曼氰基金属配合物是最大且最著名的亚铁自旋交叉化合物类别之一。在本文中,我们报道了首例含未取代1,2,3 - 三唑的亚铁霍夫曼包合物类似物,它们表现出温度诱导的自旋转变。通过磁化率测量发现,两种通式为[FeII(1,2,3 - 三唑)2MII(CN)4](M = Pt,Pd)的新型配位聚合物在190 - 225 K范围内经历了急剧的滞后自旋交叉。这两种化合物是同构的,由无限的氰基金属层构成,这些层由1,2,3 - 三唑配体支撑。在0.5至10 K min-1的不同扫描速率下,热滞回线非常稳定。这些化合物表现出强烈的热致变色效应,颜色从低自旋态的粉红色变为高自旋态的白色。我们的研究结果表明,1,2,3 - 三唑适用于制备自旋交叉霍夫曼包合物类似物,用它代替更经典的吖嗪可以有利地扩展这类配合物家族。