Abstract：
Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist in developing crystalline solids that have similar degrees of flexibility as in solution. Herein, we report the preparation of the new flexible crystalline metal complex [Cd(CF3SO3)2(4-spy)4] (4-spy=4-styrylpyridine), which contains photoreactive 4-spy ligand. Unlike traditional solids, this metal complex displays solution state-like [2+2] photocycloaddition reactivity. Specifically, UV irradiation of the crystalline material leads to formation of the same diverse array of dimers and cis isomer that are generated by photoreaction in the solution state. In addition, the photoresponsive flexibility of the solid leads to a photosalient effect and photo-induced formation of pores. The origin of the solution state-like photoreactivity of the solid is related to properties of the Cd(II) cation and fluorinated CF3SO3 anion, and the multi-orientational arrangement of the 4-spy ligands.
摘要：
柔性结晶固体响应于诸如热和光的外部刺激而表现出独特的性质。然而,在开发具有与溶液相似程度的柔性的结晶固体中存在挑战。在这里，我们报道了新的柔性晶体金属配合物[Cd（CF3SO3）2（4-spy）4]（4-spy=4-苯乙烯基吡啶）的制备，其中包含光反应性4-spy配体。与传统固体不同，这种金属配合物显示溶液状态类似的[2+2]光环加成反应性。具体来说,晶体材料的UV照射导致形成相同的不同排列的二聚体和顺式异构体,其通过在溶液状态下的光反应产生。此外,固体的光响应柔性导致光显效应和光诱导的孔形成。固体的溶液态样光反应性的起源与Cd（II）阳离子和氟化CF3SO3阴离子的性质有关，以及4-spy配体的多取向排列。
