An electron-transfer[Fe_(2)Co_(2)]square complex exhibiting unprecedented wide room-temperature hysteresis

作     者：Xin-Hua Zhao Yi-Fei Deng Jia-Tao Chen Jiong Yang Yuan-Zhu Zhang 

作者机构：Department of ChemistrySouthern University of Science and Technology(SUSTech)Shenzhen 518055China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第4期

页      面：1198-1207页

核心收录：

学科分类：0711[理学-系统科学] 081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by the National Natural Science Foundation of China(21671095,22173043) the Stable Support Plan Program of Shenzhen Natural Science Fund(20200925151834005) Shenzhen Science and Technology Program(JCYJ20220818100417037) Guangdong Basic and Applied Basic Research Foundation(2022A1515011818) 

主　　题：switchable molecules cyanometallate complexes electron transfer hysteresis structural phase transition 

摘      要：Switchable molecules with magnetic bistability that can function at standard conditions are highly desirable from the perspective of practical *** the last decade,significant progress has been made in modulating thermally induced electrontransfer-coupled spin transition(ETCST)events between diamagnetic{Fe_(LS)^(Ⅱ)(μ-CN)Co_(LS)^(Ⅲ)}and paramagnetic{Fe_(LS)^(Ⅲ)(μ-CN)-Co_(HS)^(Ⅱ)}electron configurations(named LS and HS,respectively,for short)within the Fe/Co mixed-valence cyanometallate ***,we prepared a novel[Fe_(2)Co_(2)]square complex[(pzTp)Fe(CN)_(3)Co(bnbpen)]_(2)[NO_(3)]_(2)·4CH_(3)OH·2.5H_(2)O(1·Solv)and its desolvated phase[(pzTp)Fe(CN)_(3)Co(bnbpen)]_(2)[NO_(3)]_(2)(1),obtained via single-crystal-to-single-crystal(SCSC)*** 1·Solv remaining in the diamagnetic state below room temperature exhibits an irreversible ETCST behavior accompanied by desolvation upon ***,complex 1 displays an unprecedented rate-dependent ETCST behaviour involving with two diamagnetic LS states(a dynamically favoured LS1 state and a thermodynamically favoured LS2state),between which a net one-way transition from LS1 to LS2 is accessible likely via a structural phase transition(SPT)above255 ***,two well separated transition channels(HS?LS1 at around 255 K and HS←→LS2 in the temperature range of 317-350 K)are achieved according to either fast(20 K/min)or slow rate(1 K/min),*** a moderate rate of 3 K/min,complex 1 shows a wide hysteresis of 66 K centered at 328 K,the largest yet reported for discrete Fe/Co cyanometallate *** 1 represents the first ETCST example coupled with dynamic SPT,providing a new strategy for manipulating bistability within this fascinating cyanometallate family.