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-dependent studies on two chemical series of phenoxazine compounds. In the first series (N-aryl 3,7-dibiphenyl phenoxazine), we find high sensitivity of photophysical behavior to naphthyl connectivity at its 1 versus 2 positions, including a drop in the intersystem-crossing yield (ΦISC) from 0.91 (N-1-naphthyl) to 0.54 (N-2-naphthyl), which we attribute to the establishment of an excited-state equilibrium in the singlet manifold. Drawing on the synthetic tunability afforded by phenoxazine, a modified series (N-aryl 3,7-diphenyl phenoxazine) is chosen to circumvent this equilibrium, thereby isolating the impact of naphthyl connectivity on charge-transfer energy and triplet formation. We conclude that donor–acceptor distance is a key design parameter that influences a host of excited-state and dynamical properties and can have an outsized impact on photochemical function.

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (k act ) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and N-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.