Molecular Twist-Induced Single-Crystal Isomerization and Valence Tautomeric Transitions in a Cobalt-Dioxolene Complex

Ling Tai Yue, Svetlana O. Shapovalova, Jie Sheng Hu, Maxim G. Chegerev, Yu Meng Zhao, Cheng Dong Liu, Meng Yu*, Alyona A. Starikova*, Alexander A. Guda, Zi Shuo Yao, Jun Tao*

*此作品的通讯作者

科研成果: 期刊稿件文章同行评审

2 引用 (Scopus)

摘要

A mononuclear valence tautomeric (VT) complex, [Co(pycz)2(Sq)(Cat)] (1-trans), where pycz = 9-(pyridin-4-yl)-9H-carbazole, Sq⋅ = 3,5-di-tert-butyl-semiquinonato, and Cat2− = 3,5-di-tert-butyl-catecholato, is synthesized in the trans configuration, which undergoes one-step valence tautomeric transition above room temperature. Remarkably, 1-trans can transform into its isomeric structure, [Co(pycz)2(Sq)(Sq)] (1-cis), at temperature above 350 K in a single-crystal-to-single-crystal way by in situ molecular twist, and the resulting 1-cis exhibits a pronounced two-step VT transition during magnetic measurements that is rare for mononuclear VT complexes. Such drastic solid-state structural transformation is reported in VT compounds for the first time, which is actuated by a crystal surface's melting-recrystallization induced phase transition process. DFT calculations offer an underlying mechanism suggesting a concerted bond rotation during the structural transformation. The results demonstrate an unconventional approach that realizes structural transformation of VT complexes and the control of VT performance.

源语言英语
文章编号e202401950
期刊Angewandte Chemie - International Edition
63
18
DOI
出版状态已出版 - 24 4月 2024

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Yue, L. T., Shapovalova, S. O., Hu, J. S., Chegerev, M. G., Zhao, Y. M., Liu, C. D., Yu, M., Starikova, A. A., Guda, A. A., Yao, Z. S., & Tao, J. (2024). Molecular Twist-Induced Single-Crystal Isomerization and Valence Tautomeric Transitions in a Cobalt-Dioxolene Complex. Angewandte Chemie - International Edition, 63(18), 文章 e202401950. https://doi.org/10.1002/anie.202401950