A Multifunctional Photoredox-Organocatalyst System for Small Molecule Activation

均相光氧化还原催化为传统的热促进反应提供了一种有趣的替代方法这些光化学驱动的过程在温和的反应条件下使用丰富、廉价的能源（太阳或环境光），并使用定义良好的催化剂来有效地利用光化学能。典型的光氧化还原催化剂（PRC）由RuII或IrIII配合物组成，尽管基于AuI、ReI、CuI和PtII的其他光物理活性配合物也已被探索。很少有研究系统地探索催化剂的光电性质或设计定制的prc以调整其反应性。本课题针对有机TADF化合物作为PRCs的合成、设计和应用，目标如下：1)设计和合成非常高三重态能量的PRCs；2)利用这些prc还原目前普遍不适用的芳酰氯和烷基卤化物；3)通过有机催化剂的双底物活化进一步提高反应活性；4)设计一个包含PRC和有机催化剂功能的一体化系统。

Homogeneous photoredox catalysis offers an intriguing alternative to traditional thermally-promoted reactions.1 These photochemically driven processes use an abundant, cheap energy source (the sun or ambient light) under mild reactions conditions and employ well-defined catalysts that act to efficiently harness photochemical energy. Typical photoredox catalysts (PRC) consist of RuII or IrIII complexes, though other photophysically active complexes based on AuI, ReI, CuI and PtII have all been explored. Few studies have systematically probed the optoelectronic properties of the catalysts or designed bespoke PRCs in order to tune their reactivity.This proposal targets the synthesis, design and application of organic TADF compounds as PRCs with the following goals: 1) design and synthesis of very high triplet energy PRCs; 2) utilization of these PRCs for reduction of aryl chlorides and alkyl halides that is currently generally not applicable; 3) further increase reactivity through dual substrate activation with an organocatalyst; 4) design an all-in-one system that contains both the PRC and organocatalyst functionality.