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Unidirectional Photoisomerization of Styrylpyridine for Switching the Magnetic Behavior of an Iron(II) Complex: A MLCT Pathway in Crystalline Solids

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journal contribution
posted on 16.12.2010, 00:00 by Antoine Tissot, Marie-Laure Boillot, Sébastien Pillet, Epiphane Codjovi, Kamel Boukheddaden, Latévi Max Lawson Daku
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.