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在受限条件下通过可见光敏化使偶氮苯失去平衡

Disequilibrating azobenzenes by visible-light sensitization under confinement.

作者信息

Gemen Julius, Church Jonathan R, Ruoko Tero-Petri, Durandin Nikita, Białek Michał J, Weißenfels Maren, Feller Moran, Kazes Miri, Odaybat Magdalena, Borin Veniamin A, Kalepu Rishir, Diskin-Posner Yael, Oron Dan, Fuchter Matthew J, Priimagi Arri, Schapiro Igor, Klajn Rafal

机构信息

Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 7610001, Israel.

Fritz Haber Center for Molecular Dynamics Research, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel.

出版信息

Science. 2023 Sep 22;381(6664):1357-1363. doi: 10.1126/science.adh9059. Epub 2023 Sep 21.

Abstract

Photoisomerization of azobenzenes from their stable isomer to the metastable state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to induce the -to- isomerization by using light of a desired color, including red. DESC relies on a combination of a macrocyclic host and a photosensitizer, which act together to selectively bind and sensitize -azobenzenes for isomerization. The isomer lacks strong affinity for and is expelled from the host, which can then convert additional azobenzenes to the state. In this way, the host-photosensitizer complex converts photon energy into chemical energy in the form of out-of-equilibrium photostationary states, including ones that cannot be accessed through direct photoexcitation.

摘要

偶氮苯从其稳定异构体光异构化为亚稳态是这些分子众多应用的基础。然而,该反应通常需要紫外光,这限制了其适用性。在本研究中,我们引入了受限敏化去平衡法(DESC),这是一种超分子方法,通过使用包括红光在内的所需颜色的光来诱导 - 到 - 的异构化。DESC依赖于大环主体和光敏剂的组合,它们共同作用以选择性地结合并敏化 - 偶氮苯进行异构化。 异构体对主体缺乏强亲和力并被主体排出,然后主体可以将额外的偶氮苯转化为 状态。通过这种方式,主体 - 光敏剂复合物将光子能量转化为非平衡光稳态形式的化学能量,包括那些无法通过直接光激发获得的光稳态。

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