Effects of Naphthyl Connectivity on the Photophysics of Compact Organic Charge-Transfer Photoredox Catalysts

Modular chromophoric systems with minimal electronic coupling between donor and acceptor moieties are well suited for establishing predictive relationships between molecular structure and excited-state properties. Here, we investigate the impact of naphthyl-based connectivity on the photophysics of phenoxazine-derived orthogonal donor–acceptor complexes. While compounds in this class are themselves interesting as potent organic photocatalysts useful for visible-light-driven organocatalyzed atom-transfer radical polymerization and small-molecule synthesis, many other systems (e.g., phenazine, phenothiazine, and acridinium) exploit charge-transfer excited states involving a naphthyl substituent. Therefore, aided by the facile tunability of the phenoxazine architecture, we aim to provide mechanistic insight into the effects of naphthyl connectivity that can help inform the understanding of other systems. We do so by employing time-resolved and steady-state spectroscopies, cyclic voltammetry, and temperature-...