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协同双色共价键形成的定量分析。

Quantification of Synergistic Two-Color Covalent Bond Formation.

作者信息

Hobich Jan, Feist Florian, Werner Phillip, Carroll Joshua A, Fuhr Olaf, Blasco Eva, Mutlu Hatice, Barner-Kowollik Christopher

机构信息

Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Kaiserstraße 12, 76131, Karlsruhe, Germany.

School of Chemistry and Physics, Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD 4000, Australia.

出版信息

Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413530. doi: 10.1002/anie.202413530. Epub 2024 Nov 7.

Abstract

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi-color reaction modes. One particularly powerful mode is the synergistic two-color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two-color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis-to-trans isomerization of a bridged ring-strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well-defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x-ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual-color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio . A reduced termed -that extrapolates to conditions of infinitesimal conversions-allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

摘要

对于复杂的光化学反应过程,高波长分辨反应性信息的出现使得多色反应模式得以建立。一种特别强大的模式是协同双色反应,其中两种颜色的光必须存在于同一体积元中,以实现或增强导致特定光产物的光化学反应性。在此,我们介绍一种基于二芳基茚酮环氧化物(DIO)光开关和桥连环应变偶氮苯(SA)的顺反异构化的双色协同光化学反应体系,它们分别以不同速率响应紫外光(365 nm)和可见光(430 nm),形成一种结构明确的杂环光加合物DIOSA,我们通过单晶X射线衍射(SXRD)对其结构进行了确认。为了定量捕捉双色辐照作为反应条件(如光强度)和起始物料比作为产物产率函数的有效性,我们引入了一个参数,即光化学协同比 。一个简化的 称为 - 它外推到无限小转化率的条件 - 允许比较不同反应条件下协同光化学的效率。

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