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Spin-crossover modulation via single-crystal to single-crystal photochemical [2 + 2] reaction in Hofmann-type frameworks.

ABSTRACT: This study reports the first modulation of spin-crossover (SCO) behavior via a photochemical [2 + 2] cycloaddition reaction. Here we construct two no-solvent Fe(ii)-Ag(i) bimetallic Hofmann-type frameworks, [Fe(4-spy)2{Ag(CN)2}2] (1) and [Fe(2,4-bpe)2{Ag(CN)2}2] (2) (4-spy = 4-styrylpyridine, 2,4-bpe = trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene). For 1, the dimerization of 4-spy results in a single-crystal to single-crystal (SCSC) transformation from 2D interdigitated layers to a 3D interpenetrated structure. Additionally, a 3D ? 3D structural transformation accompanied with Ag(i)-N bond breaking is achieved via the photochemical cycloaddition reaction of 2,4-bpe in 2. More importantly, both the spin transition temperatures and the SCO character are effectively modulated; thus, this approach provides a new strategy for constructing photo-responsive SCO magnetic materials.

SUBMITTER: Wang LF 

PROVIDER: S-EPMC6764279 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Spin-crossover modulation <i>via</i> single-crystal to single-crystal photochemical [2 + 2] reaction in Hofmann-type frameworks.

Wang Long-Fei LF   Zhuang Wei-Man WM   Huang Guo-Zhang GZ   Chen Yan-Cong YC   Qiu Jiang-Zhen JZ   Ni Zhao-Ping ZP   Tong Ming-Liang ML  

Chemical science 20190703 32

This study reports the first modulation of spin-crossover (SCO) behavior <i>via</i> a photochemical [2 + 2] cycloaddition reaction. Here we construct two no-solvent Fe(ii)-Ag(i) bimetallic Hofmann-type frameworks, [Fe(4-spy)<sub>2</sub>{Ag(CN)<sub>2</sub>}<sub>2</sub>] (<b>1</b>) and [Fe(2,4-bpe)<sub>2</sub>{Ag(CN)<sub>2</sub>}<sub>2</sub>] (<b>2</b>) (4-spy = 4-styrylpyridine, 2,4-bpe = <i>trans</i>-1-(2-pyridyl)-2-(4-pyridyl)ethylene). For <b>1</b>, the dimerization of 4-spy results in a singl  ...[more]

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