Abstract
Photoredox catalysis of chemical reactions, using light-activated molecules which serve as electron donors or acceptors to initiate chemical transformations under mild conditions, is finding widespread use in the synthesis of organic compounds and materials. The transition-metal-centred complexes first developed for these photoredox-catalysed applications are steadily being superseded by more sustainable and lower toxicity organic photocatalysts. While the diversity of possible structures for photoredox-active organic molecules brings benefits of design flexibility, it also presents considerable challenges for optimization of the photocatalyst molecular architecture. Transient absorption spectroscopy over timescales from the femtosecond to microsecond domains can explore the detailed mechanisms of activation and reaction of these organic photocatalysts in solution and, by linking their dynamical properties to their structures, has the potential to establish reliable design principles for future development of improved photocatalysts.
Highlights
The pharmaceutical and technological benefits of sustainable synthesis of a wide range of speciality chemicals and advanced materials are driving the fast-paced development of new synthetic strategies
Transient absorption spectroscopy over timescales from the femtosecond to microsecond domains can explore the detailed mechanisms of activation and reaction of these organic photocatalysts in solution and, by linking their dynamical properties to their structures, has the potential to establish reliable design principles for future development of improved photocatalysts
These organic photocatalysts (OPCs) can, in principle, circumvent the problems of toxicity, cost, and sustainability associated with many metal complexes but must contain chromophores activated by near-UV and visible light
Summary
The pharmaceutical and technological benefits of sustainable synthesis of a wide range of speciality chemicals and advanced materials are driving the fast-paced development of new synthetic strategies. The momentum for development of new photoredox-catalysed reaction schemes has largely relied on the electron donor and acceptor properties of excited states of transition-metal complexes such as [Ru(bpy)3]2þ and [Ir(ppy)3],1 there is growing interest in the development of organic molecules as photoredox catalysts.4,14 These organic photocatalysts (OPCs) can, in principle, circumvent the problems of toxicity, cost, and sustainability associated with many metal complexes but must contain chromophores activated by near-UV and visible light. Much reliance remains on trial-and-error modification of OPC structures to optimize their properties for specific classes of reaction This perspective argues that indepth characterization of OPC excited-state properties and electron transfer reaction rates using transient spectroscopy techniques can provide a framework for more-informed design of OPCs for a range of future chemical and materials synthesis applications
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