Kumar Kundu Bidyut, Bashar Noorul, Srivastava Prasenjit, Elles Christopher G, Sun Yujie
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio, 43221, United States.
Department of Chemistry, University of Kansas, Lawrence, KS, 66045, USA.
Chemistry. 2024 Dec 10;30(69):e202402856. doi: 10.1002/chem.202402856. Epub 2024 Oct 29.
Conventional organic photocatalysis typically relies on ultraviolet and short-wavelength visible photons as the energy source. However, this approach often suffers from competing light absorption by reactants, products, intermediates, and co-catalysts, leading to reduced quantum efficiency and side reactions. To address this issue, we developed novel organic two-photon-absorbing (TPA) photosensitizers capable of functioning under deep red and near-infrared light irradiation. Three model reactions including cyclization, Sonogashira C-C cross-coupling, and C-N cross-coupling reactions were selected to compare the performance of the new photosensitizers under both blue (427 nm) and deep red (660 nm) light irradiation. The obtained results unambiguously prove that for reactions involving blue light-absorbing reactants, products, and/or co-catalysts, deep red light source resulted in better performance than blue light when utilizing our TPA photosensitizers. This work highlights the potential of our metal-free TPA photosensitizers as a sustainable and effective solution to mitigate the competing light absorption issue in photocatalysis, not only expanding the scope of organic photocatalysts but also reducing reliance on expensive Ru/Ir/Os-based photosensitizers.
传统的有机光催化通常依赖紫外光和短波长可见光光子作为能量来源。然而，这种方法常常受到反应物、产物、中间体和助催化剂对光的竞争性吸收的影响，导致量子效率降低和副反应发生。为了解决这个问题，我们开发了新型的有机双光子吸收（TPA）光敏剂，其能够在深红色和近红外光照射下发挥作用。我们选择了包括环化反应、Sonogashira C-C交叉偶联反应和C-N交叉偶联反应在内的三个模型反应，以比较新型光敏剂在蓝光（427 nm）和深红色光（660 nm）照射下的性能。所得结果明确证明，对于涉及吸收蓝光的反应物、产物和/或助催化剂的反应，当使用我们的TPA光敏剂时，深红色光源比蓝光产生更好的性能。这项工作突出了我们的无金属TPA光敏剂作为一种可持续且有效的解决方案来减轻光催化中竞争性光吸收问题的潜力，不仅扩大了有机光催化剂的范围，还减少了对昂贵的基于钌/铱/锇的光敏剂的依赖。
