Gaikwad Shweta, Bhattacharjee Argha, Elacqua Elizabeth
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA.
Chemistry. 2025 Apr 9;31(21):e202404699. doi: 10.1002/chem.202404699. Epub 2025 Mar 11.
Photoredox catalysis has emerged as a potent means to conduct synthetic chemistry. Leveraging light to achieve challenging organic transformations has led to many developments, both of fundamental and industrial nature. Despite their potency, photoredox processes are inherently diffusion controlled, which can limit their ability to enable both reactivity and selectivity. Relevant to this is the idea of colocalizing cocatalysts in architectures that enable spatial proximity, promoting 'catalysis under confinement.' In this Concept review, we summarize recent designs and advancements using well-defined heterogeneous and homogeneous frameworks that enable dual photoredox catalysis, such as metal-organic frameworks, heterogeneous organic polymeric systems, and single-chain polymer nanoparticles (SCNPs). These advances generally stem from the material's inherent ability to enforce catalyst communication, typically resulting in expedient radical, electron, or energy transfer that accelerates reactivity. Whereas heterogeneous systems are comprehensively investigated, the design space arising from the modularity and versatility of a SCNP is quite large making the recyclable platform an intriguing candidate to investigate for confinement-enabled photoredox catalysis. We expect that both heterogeneous and homogeneous platforms systems detailed herein will continue to exhibit superior performance, while underscoring the importance of confinement to tackle diffusion-limited reactions.
光氧化还原催化已成为进行合成化学的一种有效手段。利用光来实现具有挑战性的有机转化已带来了许多基础性和工业性的发展。尽管光氧化还原过程具有强大的能力，但它们本质上是受扩散控制的，这可能会限制其实现反应性和选择性的能力。与此相关的是将助催化剂共定位在能够实现空间接近的结构中的想法，从而促进“受限条件下的催化”。在这篇概念综述中，我们总结了近期使用定义明确的异质和均质框架实现双光氧化还原催化的设计和进展，例如金属有机框架、异质有机聚合物体系和单链聚合物纳米颗粒（SCNP）。这些进展通常源于材料强制催化剂相互作用的固有能力，通常会导致便捷的自由基、电子或能量转移，从而加速反应性。虽然对异质体系进行了全面研究，但SCNP的模块化和多功能性所产生的设计空间非常大，这使得可回收平台成为研究受限光氧化还原催化的一个有趣候选对象。我们预计本文详述的异质和均质平台体系将继续展现出卓越性能，同时强调受限条件对于解决扩散受限反应的重要性。
