Modulation of Acridinium Organophotoredox Catalysts Guided by Photophysical Studies

Abstract

Control over redox states and spin multiplicity of photocatalysts throughout a catalytic cycle is crucial for selective and efficient photocatalytic processes. However, the rational design of photocatalysts is often hampered by the mechanistic complexity and low modularity of the catalyst structure. Herein, we demonstrate a photophysical study of diverging photocatalytic pathways that guides the design of organic acridinium catalysts to complement polypyridyl transition metal systems. A combined halogen–metal exchange/directed ortho-metalation provides reagents for a broad range of modular acridinium catalysts with fine-tuned photophysical and photochemical properties such as excited-state lifetimes, redox potentials, and photostabilities poised to refine organocatalytic photoredox methodology.