Kitase Kosuke, Akahoshi Daisuke, Kitazawa Takafumi
Department of Chemistry, Toho University, Chiba 274-8510, Japan.
Department of Physics, Toho University, Chiba 274-8510, Japan.
Inorg Chem. 2021 Apr 5;60(7):4717-4722. doi: 10.1021/acs.inorgchem.0c03655. Epub 2021 Mar 10.
The spin-crossover (SCO) phenomenon is an active area of research. This paper describes the synthesis of an Fe-Ag Hofmann-type complex, {Fe(4-methylpyrimidine)[Ag(CN)]}, which demonstrates a one-step SCO and single-layer Hofmann-type structure with Ag-N interactions and no Ag-Ag interactions, which is strikingly different from the previously synthesized complex {Fe(4-methylpyrimidine)[Au(CN)]} that contains Au-Au interactions and no Au-N interactions. This difference can be explained in terms of the lack of relativistic effect in the Ag atoms and the different cooperative effects caused by their different structures. A scan-rate-dependent hysteresis is observed using magnetic measurement whereas not using Fe Mössbauer spectroscopy, suggesting that the spin transition is relatively slow.
自旋交叉（SCO）现象是一个活跃的研究领域。本文描述了一种铁-银霍夫曼型配合物{Fe(4-甲基嘧啶)[Ag(CN)]}的合成，该配合物展示了一步自旋交叉和具有Ag-N相互作用而无Ag-Ag相互作用的单层霍夫曼型结构，这与先前合成的含有Au-Au相互作用而无Au-N相互作用的配合物{Fe(4-甲基嘧啶)[Au(CN)]}显著不同。这种差异可以从银原子中缺乏相对论效应以及由其不同结构引起的不同协同效应方面来解释。使用磁性测量观察到了扫描速率依赖性滞后现象，而使用铁穆斯堡尔光谱则未观察到，这表明自旋转变相对较慢。
