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光控破坏与组装:在两种不同组成的笼型配合物之间进行切换。

Light-Controlled Destruction and Assembly: Switching between Two Differently Composed Cage-Type Complexes.

机构信息

Otto-Diels-Institute of Organic Chemistry, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118, Kiel, Germany.

出版信息

Angew Chem Int Ed Engl. 2023 Jan 2;62(1):e202212571. doi: 10.1002/anie.202212571. Epub 2022 Nov 29.

Abstract

We report on two regioisomeric, diazocine ligands 1 and 2 that can both be photoswitched between the E- and Z-configurations with violet and green light. The self-assembly of the four species (1-Z, 1-E, 2-Z, 2-E) with Co ions was investigated upon changing the coordination vectors as a function of the ligand configuration (E vs Z) and regioisomer (1 vs 2). With 1-Z, Co (1-Z) was self-assembled, while a mixture of ill-defined species (oligomers) was observed with 2-Z. Upon photoswitching with 385 nm to the E configurations, the opposite was observed with 1-E forming oligomers and 2-E forming Co (2-E) . Light-controlled dis/assembly was demonstrated in a ligand competition experiment with sub-stoichiometric amounts of Co ions; alternating irradiation with violet and green light resulted in the reversible transformation between Co (1-Z) and Co (2-E) over multiple cycles without significant fatigue by photoswitching.

摘要

我们报告了两种区域异构的二氮杂环丁烷配体 1 和 2,它们都可以用紫光和绿光在 E-和 Z-构型之间进行光切换。研究了四种物种(1-Z、1-E、2-Z、2-E)与 Co 离子的自组装,其配位矢量随配体构型(E 对 Z)和区域异构体(1 对 2)而变化。对于 1-Z,形成了 Co(1-Z);而对于 2-Z,则观察到了不明成分的物种(低聚物)的混合物。用 385nm 的光切换到 E 构型时,观察到相反的情况,即 1-E 形成低聚物,而 2-E 形成 Co(2-E)。在配体竞争实验中,用亚化学计量的 Co 离子进行了光控组装/解组装的演示;交替用紫光和绿光照射,导致 Co(1-Z)和 Co(2-E)之间的可逆转化,在多次循环中没有因光切换而出现明显的疲劳。

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