Spin-crossover modulation via single-crystal to single-crystal photochemical [2 2] reaction in Hofmann-type frameworks
Spin-crossover modulation via single-crystal to single-crystal photochemical [2 2] reaction in Hofmann-type frameworks
复制标题
通过霍夫曼型框架中的单晶到单晶光化学 [2 2] 反应进行自旋交叉调制
DOI：
10.1039/c9sc02274k
复制
发表时间：
2019
期刊：
影响因子：
8.4
通讯作者：
Tong Ming Liang
中科院分区：
文献类型：
--
作者：
Wang Long Fei;Zhuang Wei Man;Huang Guo Zhang;Chen Yan Cong;Qiu Jiang Zhen;Ni Zhao Ping;Tong Ming Liang
本研究首次报道了通过光化学[2 + 2]环加成反应对自旋交叉（SCO）行为的调制。本文构建了两个非溶剂型Fe（II）-Ag（I）-Hofmann骨架[Fe（4-spy）2{Ag（CN）2}2]（1）和[Fe（2，4-bpe）2{Ag（CN）2}2]（2）（4-spy = 4-苯乙烯基吡啶，2，4-bpe =反式-1-（2-吡啶基）-2-（4-吡啶基）乙烯）。对于1，4-spy的二聚化导致从2D交叉层到3D互穿结构的单晶到单晶（SCSC）转变。此外，通过2，4-bpe在2.更重要的是，自旋转变温度和SCO字符都得到了有效的调制，因此，这种方法提供了一种新的策略，构建光响应SCO磁性材料。
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.