Kamilya Sujit, Ghosh Subrata, Li Yanling, Dechambenoit Pierre, Rouzières Mathieu, Lescouëzec Rodrigue, Mehta Sakshi, Mondal Abhishake
Solid State and Structural Chemistry Unit, Indian Institute of Science, Sir C. V. Raman Road, Bangalore 560012, India.
Institut Parisien de Chimie Moléculaire, Sorbonne Université, CNRS, UMR 8232, 4 place Jussieu, Paris 750005, France.
Inorg Chem. 2020 Sep 8;59(17):11879-11888. doi: 10.1021/acs.inorgchem.0c02053. Epub 2020 Aug 17.
A cyanide-bridged [FeCo] molecular square complex, {[Fe(Tp)(CN)][Co()]}(BF)·2CHCN·6HO [; Tp = hydrotris(pyrazol-1-yl)borate and = bis(1-ethyl-1-imidazol-2-yl)ketone], has been synthesized and characterized fully by single-crystal X-ray diffraction, (photo)magnetic measurements, optical reflectivity, and other physical measurements. exhibits a two-step metal-to-metal electron-transfer (MMET)-induced spin transition accompanied by thermal hysteresis (↑ = 332 and 407 K and ↓ = 320 and 405 K, respectively), converting the low-temperature diamagnetic {Fe-CN-Co} ground state into the high-temperature paramagnetic {Fe-CN-Co} state. Additionally, displays reversible photoinduced MMET under light irradiation (ON mode using 808 nm laser light and OFF mode using 532 nm laser light), as confirmed by optical reflectivity and (photo)magnetic measurements. The photoinduced paramagnetic metastable state relaxes back to the diamagnetic ground state at 91 K ( = 91 K). Astonishingly, also exhibits a 27 K wide light-induced thermal hysteresis below 100 K. The overall results show that is a multistimuli-responsive bistable material that exhibits reversible switching between the diamagnetic state, {Fe-CN-Co}, and the paramagnetic state, {Fe-CN-Co}, under the application of temperature and light.
一种氰基桥联的[FeCo]分子方形配合物{[Fe(Tp)(CN)]Co()·2CHCN·6HO [；Tp = 氢三(吡唑-1-基)硼酸酯， = 双(1-乙基-1-咪唑-2-基)酮]已通过单晶X射线衍射、(光)磁测量、光反射率和其他物理测量进行了全面合成和表征。该配合物表现出两步金属到金属电子转移(MMET)诱导的自旋转变，并伴有热滞回(↑分别为332 K和407 K，↓分别为320 K和405 K)，将低温抗磁性的{Fe-CN-Co}基态转变为高温顺磁性的{Fe-CN-Co}态。此外，通过光反射率和(光)磁测量证实，该配合物在光照射下显示可逆的光诱导MMET(使用808 nm激光的开启模式和使用532 nm激光的关闭模式)。光诱导的顺磁性亚稳态在91 K( = 91 K)时弛豫回到抗磁性基态。令人惊讶的是，该配合物在100 K以下还表现出27 K宽的光诱导热滞回。总体结果表明，该配合物是一种多刺激响应双稳态材料，在温度和光的作用下，在抗磁性状态{Fe-CN-Co}和顺磁性状态{Fe-CN-Co}之间表现出可逆切换。
