Mononuclear Fe(II) Complexes Based on the Methylpyrazinyl-Diamine Ligand: Chemical-, Thermo- and Photocontrol of Their Magnetic Switchability,Inorganic Chemistry

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Mononuclear Fe(II) Complexes Based on the Methylpyrazinyl-Diamine Ligand: Chemical-, Thermo- and Photocontrol of Their Magnetic Switchability
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-09-22 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01430
Xue Liu ₁ , Jian Zhou ₁ , Xin Bao ₁ , Zheng Yan ₂ , Guo Peng ₃ , Mathieu Rouzières _{4,

5} , Corine Mathonière _{6,

7} , Jun-Liang Liu _{4,

5} , Rodolphe Clérac _{4,

5}

Affiliation

Two new mononuclear Fe(II) complexes, [Fe(^2MeL_pz)(NCX)₂] (L = N,N′-dimethyl-N,N′-bis((pyrazin-2-yl)methyl)-1,2-ethanediamine and X = S (1), BH₃ (2)), have been synthesized and characterized by single-crystal X-ray diffraction, magnetic, optical reflectivity, and photomagnetic measurements. They have similar FeN₆ coordination environments offered by the tetradentate ligand with a cis-α conformation and two NCX^– coligands in cis positions. However, 1 and 2 have different molecular arrangements and crystal packings, and are isolated in orthorhombic Pbnb and monoclinic C2/c space groups, respectively. 1 remains in a high spin state (S = 2) over all temperatures while 2 undergoes a spin transition around 168 K with a small thermal hysteresis of about 0.4 K (at a temperature scan rate of 1.3 K min^–1). This phase transition, which can also be optically detected due to the associated marked change of the sample color, occurs between two structurally characterized phases, which exhibit Fe(II) complexes in their high spin and low spin states at high and low temperatures, respectively. The reversible photoswitching between these two states has also been confirmed at low temperatures using well separated wavelength irradiations.

中文翻译：

基于甲基吡嗪基-二胺配体的单核Fe（II）配合物：磁性切换的化学，热和光控制

两个新的单核Fe（II）配合物[Fe（^2Me L _pz）（NCX）₂ ]（L = N，N'-二甲基-N，N'-双（（吡嗪-2-基）甲基）-1，已经合成了2-乙二胺和X = S（1），BH ₃（2）），并通过单晶X射线衍射，磁，光反射率和光磁测量对其进行了表征。它们有相似的汾酒₆所提供协调的环境中四齿配体与顺-α构象和两个NCX ^-共配的顺位。但是，1和2具有不同的分子排列和晶体堆积，并且分别位于正交晶的Pbnb和单斜C 2 / c空间群中。1在所有温度下均保持高自旋状态（S = 2），而2在168 K左右经历自旋转变，并具有约0.4 K的较小热滞（在1.3 K min的温度扫描速率下^–1）。这种相变也可以通过样品颜色的相关显着变化进行光学检测，发生在两个结构特征相之间，在高温和低温下，它们分别在高自旋和低自旋状态下表现出Fe（II）配合物。这两种状态之间的可逆光开关也已在低温下使用良好分开的波长辐照进行了确认。

更新日期：2017-09-22

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