Solution State‐Like Reactivity of a Flexible Crystalline Werner‐Type Metal Complex

Author:

Zhang Yunya1,Zheng Xin2,Saito Yuki2,Takeda Takashi134,Hoshino Norihisa5,Takahashi Kiyonori6,Nakamura Takayoshi67,Akutagawa Tomoyuki13,Noro Shin‐ichiro2ORCID

Affiliation:

1. Graduate School of Engineering Tohoku University Sendai 980-8579 Japan

2. Faculty of Environmental Earth Science Hokkaido University Sapporo 060-0810 Japan

3. Institute of Multidisciplinary Research for Advanced Materials (IMRAM) Tohoku University Sendai 980-8577 Japan

4. Present address Department of Chemistry Faculty of Science Shinshu University Matsumoto 390-8621 Japan

5. Department of Materials Science and Technology Faculty of Engineering Niigata University Niigata 950-2181 Japan

6. Research Institute for Electronic Science Hokkaido University Sapporo 001-0020 Japan

7. Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University Higashi-hiroshima 739-8526 Japan

Abstract

AbstractFlexible 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.

Funder

Iketani Science and Technology Foundation

Moonshot Research and Development Program

Publisher

Wiley

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