Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence{Fe^(Ⅲ)_(4)Fe^(Ⅱ)_(4)}Cubes  

作　　者：Maolin You De-Xuan Gan Yi-Fei Deng Dong Shao Yin-Shan Meng Xiao-Yong Chang Yuan-Zhu Zhang 

机构地区：[1]Department of Chemistry,Southern University of Science and Technology(SUSTech),Shenzhen 518055 [2]Department of Chemistry,National University of Singapore,Singapore 117543 [3]State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024

出　　处：《CCS Chemistry》2022年第7期2452-2459,共8页中国化学会会刊（英文）

基　　金：supported by the Stable Support Plan Program of Shenzhen Natural Science Fund(no.20200925151834005);the National Natural Science Foundation of China(nos.21671095 and 21901108).

摘　　要：The engineering of switchable moleculeswith dramatic magnetic change is currently among themost active areas in chemical research.Here,two cyanide-bridged mixed-valence{Fe^(Ⅲ)_(4)Fe^(Ⅱ)_(4)}cubes were prepared,both of which,interestingly,exhibited reversible thermally inducedmetal-to-metal charge transfer(MMCT)behavior between{Fe^(Ⅲ,LS)_(4)Fe^(Ⅱ,HS)_(4)}and{Fe^(Ⅱ,LS)_(4)Fe^(Ⅲ,HS)_(4)}configurations with the transition temperature(T_(1/2))of 274 and 230 K,respectively.These cubes provided a rare example of discrete homometallic complexes exhibiting the reversible MMCT rather than spin crossover behavior.In stark contrast to the heterometallic Fe/Co system,in which the charge transfer(CT)and spin transition(ST)processes occur simultaneously,the detailed structural and Mössbauer spectroscopy analyses confirmed the CT property without involving ST.In addition,both of these cubes showed excellent redox flexibility in solutionwith seven quasi accessible electronic states.

关 键 词：charge transfer Prussian blue analogs cyanide complexes MIXED-VALENCE molecular switches 

分 类 号：TN2[电子电信—物理电子学]