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

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Abstract

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 {FeIILS(μ-CN)CoIIILS} and paramagnetic {FeLS(μ-CN)-CoIIHS} 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)3Co(bnbpen)]2[NO3]2·4CH3OH·2.5H2O (1·Solv) and its desolvated phase [(pzTp)Fe(CN)3Co(bnbpen)]2[NO3]2 (1), obtained via single-crystal-to-single-crystal (SCSC) transformation. Complex 1·Solv 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.

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Acknowledgements

This work was 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), and Guangdong Basic and Applied Basic Research Foundation (2022A1515011818). We thank Dr. Bin Chen from Soochow University for UV-vis NIR measurements.

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  1. Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China

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

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  1. Xin-Hua Zhao
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  2. Yi-Fei Deng
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  3. Jia-Tao Chen
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Correspondence to Yuan-Zhu Zhang.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Zhao, XH., Deng, YF., Chen, JT. et al. An electron-transfer [Fe2Co2] square complex exhibiting unprecedented wide room-temperature hysteresis. Sci. China Chem. 67, 1198–1207 (2024). https://doi.org/10.1007/s11426-023-1835-y

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