Unidirectional Photoisomerization of Styrylpyridine for Switching the Magnetic Behavior of an Iron(II) Complex: A MLCT Pathway in Crystalline Solids
Unidirectional Photoisomerization of Styrylpyridine for Switching the Magnetic Behavior of an Iron(II) Complex: A MLCT Pathway in Crystalline Solids
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DOI：
10.1021/jp106583f
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发表时间：
2010-11
影响因子：
3.7
通讯作者：
A. Tissot;M. Boillot;S. Pillet;E. Codjovi;K. Boukheddaden;L. M. L. Daku-L.-M.-L.-Daku-16183618
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文献类型：
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作者：
A. Tissot;M. Boillot;S. Pillet;E. Codjovi;K. Boukheddaden;L. M. L. Daku-L.-M.-L.-Daku-16183618
首次在结晶固体中研究了两种铁(II)−苯乙烯基吡啶骨架 Fe(stpy)4(NCSe)2 (stpy = 4-苯乙烯基吡啶)的光反应性。研究表明，二苯乙烯类化合物的定量顺式至反式异构化发生在无机固体的受限环境中。光致变色反应是由高自旋全顺式配合物的金属到配体电荷转移吸收的可见激发驱动的。固态转变伴随着晶胞体积的增加和非晶化。有趣的是，当温度降低时，通过照射高自旋全顺式反应物形成的光产物会经历自旋转换。这一观察结果与受限环境中的“配体驱动的光诱导自旋变化”效应有关。
The photoreactivity of two iron(II)−styrylpyridine frameworks Fe(stpy)4(NCSe)2 (stpy = 4-styrylpyridine) has been investigated for the very first time in a crystalline solid. A quantitative cis-to-trans isomerization of stilbenoids is shown to occur in the confined environment of the inorganic solid. The photochromic reaction was driven by a visible excitation into the metal-to-ligand charge transfer absorption of the high-spin all-cis complex. The solid-state transformation is accompanied by a unit-cell volume increase and an amorphization. Interestingly, the photoproduct formed by irradiating the high-spin all-cis reactant undergoes a spin conversion when the temperature is decreased. This observation is related to the “ligand-driven light-induced spin change” effect in a constrained environment.