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Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-06-02 , DOI: 10.1002/anie.202007327
Szymon Chorazy 1 , Tomasz Charytanowicz 1 , Dawid Pinkowicz 1 , Junhao Wang 2 , Koji Nakabayashi 2 , Stephen Klimke 3 , Franz Renz 3 , Shin-Ichi Ohkoshi 2 , Barbara Sieklucka 1
Affiliation  

A two‐step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3‐CNpy)2][Re(CN)8]}⋅H2O (1) (3‐CNpy=3‐cyanopyridine) assembly consisting of cyanido‐bridged FeII‐ReV square grid sheets bonded by Cs+ ions. The presence of two non‐equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non‐covalent interlayer interactions involving Cs+, [ReV(CN)8]3− ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin‐transition phenomenon could be tuned by an external pressure giving the room‐temperature range of SCO, as well as by visible‐light irradiation, inducing an efficient recovery of the high‐spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

中文翻译:

Octacyanidorhenate(V)离子作为迟滞两步铁(II)自旋交联的有效连接子,可通过温度,光和压力进行切换。

两步滞后的Fe II自旋交叉(SCO)的效果是在编程的层叠铯{的[Fe(3- CNpy)实现2 ] [回复(CN)8 ]}⋅H 2 O(1)(3- CNpy = 3氰基吡啶)组件组成cyanido桥联的Fe II -Re V由Cs的接合方形网格薄板+离子。两个非等价的Fe II位点的存在以及二维双金属配位网络与涉及Cs +,[Re V(CN)8 ] 3−的非共价层间相互作用的结合离子和3-CNpy配体会导致两步热SCO的发生,并具有很强的协同性,从而产生双热滞回线。产生的自旋转变现象可以通过在SCO室温范围内的外部压力以及可见光照射来调节,从而在低温下有效恢复高自旋Fe II态。我们证明八氰基苯甲酸(V)离子是一种出色的金属配体,可诱导协同的多步,多开关Fe II SCO效应。
更新日期:2020-06-02
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