Hobich Jan, Feist Florian, Werner Phillip, Carroll Joshua A, Fuhr Olaf, Blasco Eva, Mutlu Hatice, Barner-Kowollik Christopher
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.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413530. doi: 10.1002/anie.202413530. Epub 2024 Nov 7.
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.
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。
