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首页> 外文期刊>Chemistry: A European journal >Photomagnetism of a Series of Dinuclear Iron(II) Complexes
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Photomagnetism of a Series of Dinuclear Iron(II) Complexes

机译：一系列双核铁（II）配合物的光磁性

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摘要

This paper describes the photomagnetic properties of a series of binuclear iron (II) complexes belonging to the [{Fe(NCS)(py-X)}(2)(bpypz)(2)] family (NCS=thiocyanate; py=pyridine; bpypz=3,5bis(pyridine-2-yl)pyrazolate; and py-X=4-Mepy (1), py (3), 3-Mepy (4), 3-Clpy (5), and 3-Brpy (6)). All of these complexes display a complete thermal spin transition centred between 100 and 150 K, and undergo the light-induced excited-spin-state strapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. For all of the complexes, it has been found that the T-(LIESST) curves at low temperature are close to the antiferromagnetic response of the [{Fe(NCS)(3,5-dmpy)}(2)-(bpypz)(2)] (3,5-dmpy=3,5-dimethylpyridine) (7) complex that is characterised by two iron (II) metal ions in a HS electronic configuration, giving some evidence of a quantitative low spin-low spin -> high spin-high spin (LS-LS -> HS-HS) photoconversion process. Depending on the nature of the cooperativity, the kinetics have been treated with stretched exponential, simply exponential, or sigmoidal models. Interestingly, this series of dinuclear complexes follows a previously proposed linear relationship between the T(LIESST) and their thermal spin transition temperatures T-1/2: T(LIESST)=T-0-0.3T(1/2). T-0 for these compounds is equal to 100 K. Based on this, and by using the empirical linear relationship found between the thermal spin transition and the Hammett constant, the HS-HS properties of complex 7 have been understood as a reflection of the physical impossibility that the T(LIESST) was higher than T-1/2. The close vicinity of the thermal spin-crossover phenomenon of 7 has been successfully checked by applying hydrostatic pressure.
机译：本文描述了属于[{Fe（NCS）（py-X）}（2）（bpypz）（2）]族（NCS =硫氰酸盐; py =吡啶）的一系列双核铁（II）配合物的光磁特性; bpypz = 3,5bis（吡啶-2-基）吡唑酸酯;和py-X = 4-Mepy（1），py（3），3-Mepy（4），3-Clpy（5）和3-Brpy （6））。所有这些络合物均表现出以100 K至150 K为中心的完整热自旋跃迁，并在低温下经历光诱导的激发自旋带（LIESST）效应。已确定每种化合物的光诱导高自旋态的T（LIESST）弛豫温度。对于所有配合物，已发现低温下的T-（LIESST）曲线接近[{Fe（NCS）（3,5-dmpy）}（2）-（bpypz）的反铁磁响应（2）]（3,5-dmpy = 3,5-二甲基吡啶）（7）络合物，其特征在于两个铁（II）金属离子呈HS电子构型，提供了定量低自旋-低自旋的证据- >高自旋-高自旋（LS-LS-> HS-HS）光转换过程。根据协作性的性质，动力学已使用扩展的指数模型，简单的指数模型或S型模型进行了处理。有趣的是，这一系列双核配合物遵循先前提出的T（LIESST）与它们的热自旋转变温度T-1 / 2：T（LIESST）= T-0-0.3T（1/2）之间的线性关系。这些化合物的T-0等于100K。基于此，并利用热自旋跃迁和Hammett常数之间的经验线性关系，将配合物7的HS-HS特性理解为是T（LIESST）高于T-1 / 2的物理可能性。通过施加静水压力已成功检查了7的热自旋交叉现象的附近。

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