An electron-transfer [Fe₂Co₂] square complex exhibiting unprecedented wide room-temperature hysteresis

Zhao, Xin-Hua; Deng, Yi-Fei; Chen, Jia-Tao; Yang, Jiong; Zhang, Yuan-Zhu

2024-04-01

10.1007/s11426-023-1835-y

SCIENCE CHINA-CHEMISTRY   影响因子和分区

1674-7291

1869-1870

Switchable molecules with magnetic bistability that can function at standard conditions are highly desirable from the perspective of practical applications. Over the last decade, significant progress has been made in modulating thermally induced electron-transfer-coupled spin transition (ETCST) events between diamagnetic {Fe-LS(II)(mu-CN)Co-LS(III)} and paramagnetic {Fe-LS(III)(mu-CN)-Co-HS(II)} electron configurations (named LS and HS, respectively, for short) within the Fe/Co mixed-valence cyanometallate complexes. Herein, we prepared a novel [Fe2Co2] square complex [(pzTp)Fe(CN)(3)Co(bnbpen)](2)[NO3](2)4CH(3)OH2.5H(2)O (1Solv) and its desolvated phase [(pzTp)Fe(CN)(3)Co(bnbpen)](2)[NO3](2) (1), obtained via single-crystal-to-single-crystal (SCSC) transformation. Complex 1Solv remaining in the diamagnetic state below room temperature exhibits an irreversible ETCST behavior accompanied by desolvation upon heating. Notably, complex 1 displays an unprecedented rate-dependent ETCST behaviour involving with two diamagnetic LS states (a dynamically favoured LS1 state and a thermodynamically favoured LS2 state), between which a net one-way transition from LS1 to LS2 is accessible likely via a structural phase transition (SPT) above 255 K. Consequently, 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), respectively. At 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 complexes. Complex 1 represents the first ETCST example coupled with dynamic SPT, providing a new strategy for manipulating bistability within this fascinating cyanometallate family.

switchable molecules cyanometallate complexes electron transfer hysteresis structural phase transition

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China["21671095","22173043"] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925151834005] ; Shenzhen Science and Technology Program[JCYJ20220818100417037] ; Guangdong Basic and Applied Basic Research Foundation[2022A1515011818]

Chemistry

Chemistry, Multidisciplinary

WOS:001182461600001

SCIENCE PRESS

Web of Science

Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Zhao, Xin-Hua,Deng, Yi-Fei,Chen, Jia-Tao,et al. An electron-transfer [Fe₂Co₂] square complex exhibiting unprecedented wide room-temperature hysteresis[J]. SCIENCE CHINA-CHEMISTRY,2024,67(4).

Zhao, Xin-Hua,Deng, Yi-Fei,Chen, Jia-Tao,Yang, Jiong,&Zhang, Yuan-Zhu.(2024).An electron-transfer [Fe₂Co₂] square complex exhibiting unprecedented wide room-temperature hysteresis.SCIENCE CHINA-CHEMISTRY,67(4).

Zhao, Xin-Hua,et al."An electron-transfer [Fe₂Co₂] square complex exhibiting unprecedented wide room-temperature hysteresis".SCIENCE CHINA-CHEMISTRY 67.4(2024).