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Reversible on-off switching of spin-crossover behavior via photochemical [2+2] cycloaddition reaction

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Abstract

Herein, we report the first example showing the reversible on-off switching of spin-crossover (SCO) property by solid state photochemical [2+2] reaction. The ultraviolet (UV) light-induced [2+2] cycloaddition reaction of 3-spy ligands in a two-dimensional (2D) Hofmann-type framework [Fe(3-spy)2{Pd(CN)4}] (1, 3-spy=3-styrylpyridine), which shows a hysteretic two-step SCO behavior, gives a 3D Hofmann-type framework [Fe(rctt-3-ppcb){Pd(CN)4}] (2, rctt-3-ppcb=rctt-1,3-bis(3-pyridyl)-2,4-bis(phenyl)cyclobutane, r=reference group, c=cis and t=trans) accompanied with the disappearing of SCO properties. Moreover, upon heating at 250 °C for 12 h, the rctt-3-ppcb ligand in 2 could be partially dedimerized to 3-spy with 68% completion through single-crystal-to-single-crystal (SCSC) transformation, giving the annealing complexes [Fe(3-spy)1.36(rctt-3-ppcb)0.32{Pd(CN)4}] (3) which display an incomplete SCO behavior. The 2 ⇌ 3 interconversion is successfully achieved via continuous UV irradiation and thermal annealing, demonstrating the effectiveness of photochemical [2+2] reaction on switching on-off SCO properties.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2018YFA0306001), the National Natural Sciences Foundation of China (21773316, 21801258, 21821003), and the Pearl River Talent Plan of Guangdong (2017BT01C161).

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Authors and Affiliations

  1. Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China

    Long-Fei Wang, Bang-Heng Lv, Feng-Tai Wu, Guo-Zhang Huang, Ze-Yu Ruan, Yan-Cong Chen, Zhao-Ping Ni & Ming-Liang Tong

  2. School of Nuclear Science and Technology, University of South China, Hengyang, 421001, China

    Min Liu

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  1. Long-Fei Wang
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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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Wang, LF., Lv, BH., Wu, FT. et al. Reversible on-off switching of spin-crossover behavior via photochemical [2+2] cycloaddition reaction. Sci. China Chem. 65, 120–127 (2022). https://doi.org/10.1007/s11426-021-1093-2

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