Kamilya Sujit, Mehta Sakshi, Lescouëzec Rodrigue, Li Yanling, Pechousek Jiri, Semwal Mohini, Mondal Abhishake
Solid State and Structural Chemistry Unit, Indian Institute of Science, Sir C. V. Raman Road, Bangalore-560012, India.
Sorbonne Université, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, 4 place Jussieu, Paris 750005, France.
Dalton Trans. 2023 Aug 8;52(31):10700-10707. doi: 10.1039/d3dt01615c.
A two-step thermo-induced spin-state switching was observed in a cyanide-bridged [FeFe] molecular square complex, {[Fe(pzTp)(CN)][Fe(L)]}[Fe(pzTp)(CN)]·4CHOH·2HO [1·4MeOH·2HO; pzTp = tetrakis(pyrazol-1-yl)borate and L = bis(1-ethylimidazol-2-yl)ketone (bik*)], which was characterized fully by single-crystal X-ray diffraction, (photo)magnetic measurements, and spectroscopic techniques. 1·4MeOH·2HO exhibited a two-step thermo-induced spin transition with (1) ↑ = 306 K and (2) ↑ = 370 K converting the low-temperature ground state, {(FeIIILS)(FeIILS)} into the high-temperature state, {(FeIIILS)(FeIIHS)} a stable intermediate phase. The desolvated phase, 1 also exhibited a gradual but reversible thermo-induced spin state change with a value of 190 K, significantly shifted to a lower temperature. It also exhibited photo-induced spin-state switching at 20 K with the value of 60 K.
在一个氰基桥联的[FeFe]分子方形配合物{[Fe(pzTp)(CN)][Fe(L)]}[Fe(pzTp)(CN)]·4CHOH·2HO [1·4MeOH·2HO；pzTp = 四(吡唑-1-基)硼酸酯，L = 双(1-乙基咪唑-2-基)酮(bik*)]中观察到了两步热诱导自旋态切换，该配合物通过单晶X射线衍射、(光)磁测量和光谱技术进行了全面表征。1·4MeOH·2HO表现出两步热诱导自旋转变，其中(1)↑ = 306 K，(2)↑ = 370 K，将低温基态{(FeIIILS)(FeIILS)}转变为高温态{(FeIIILS)(FeIIHS)}以及一个稳定的中间相。去溶剂化相1也表现出逐渐但可逆的热诱导自旋态变化，其值为190 K，显著向较低温度偏移。它在20 K时还表现出光诱导自旋态切换，其值为60 K。
