Zhang Yunya, Zheng Xin, Saito Yuki, Takeda Takashi, Hoshino Norihisa, Takahashi Kiyonori, Nakamura Takayoshi, Akutagawa Tomoyuki, Noro Shin-Ichiro
Graduate School of Engineering, Tohoku University, Sendai, 980-8579, Japan.
Faculty of Environmental Earth Science, Hokkaido University, Sapporo, 060-0810, Japan.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202407924. doi: 10.1002/anie.202407924. Epub 2024 Aug 2.
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(CFSO)(4-spy)] (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 CFSO anion, and the multi-orientational arrangement of the 4-spy ligands.
柔性晶体固体在响应热和光等外部刺激时表现出独特的性质。然而，开发具有与溶液中相似程度柔性的晶体固体存在挑战。在此，我们报告了新型柔性晶体金属配合物[Cd(CFSO)(4 - spy)]（4 - spy = 4 - 苯乙烯基吡啶）的制备，其含有光反应性的4 - spy配体。与传统固体不同，这种金属配合物表现出类似溶液状态的[2 + 2]光环加成反应性。具体而言，对该晶体材料进行紫外线照射会导致形成与溶液状态下光反应产生的相同多样的二聚体和顺式异构体阵列。此外，固体的光响应柔性导致光显著效应和光诱导的孔形成。该固体类似溶液状态的光反应性的起源与Cd(II)阳离子和氟化CFSO阴离子的性质以及4 - spy配体的多取向排列有关。
