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探索对称磷杂烯烃开关的隐藏光异构化

Probing the Hidden Photoisomerization of a Symmetric Phosphaalkene Switch.

作者信息

Deka Rajesh, Steen Jorn D, Hilbers Michiel F, Roeterdink Wim G, Iagatti Alessandro, Xiong Ruisheng, Buma Wybren Jan, Di Donato Mariangela, Orthaber Andreas, Crespi Stefano

机构信息

Department of Chemistry-Ångström Laboratory, Uppsala University Box 523, 751 20, Uppsala, Sweden.

Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.

出版信息

Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202419943. doi: 10.1002/anie.202419943. Epub 2024 Dec 13.

Abstract

In this study, we present the synthesis and analysis of a novel, air-stable, and solvent-resistant phosphaalkene switch. Using this symmetric switch, we have demonstrated degenerate photoisomerization experimentally for the first time. With a combination of photochemical-exchange NMR spectroscopy, ultrafast transient absorption spectroscopy, and quantum chemical calculations, we elucidate the isomerization mechanism of this symmetric phosphaalkene, comparing it to two other known molecules belonging to this class. Our findings highlight the critical role of the isolobal analogy between C=P and C=C bonds in governing nanoscale molecular motion and break new ground for our understanding of light-induced molecular processes in symmetric heteroalkene systems.

摘要

在本研究中,我们展示了一种新型、空气稳定且耐溶剂的磷烯开关的合成与分析。使用这种对称开关,我们首次通过实验证明了简并光异构化。结合光化学交换核磁共振光谱、超快瞬态吸收光谱和量子化学计算,我们阐明了这种对称磷烯的异构化机制,并将其与该类别的其他两个已知分子进行了比较。我们的研究结果突出了C=P和C=C键之间等瓣相似性在控制纳米级分子运动中的关键作用,并为我们理解对称杂烯烃系统中的光诱导分子过程开辟了新的途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2872/11773101/d56a424d0430/ANIE-64-e202419943-g001.jpg

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