Orientational Dependence of Cofacial Porphyrin-Quinone Electronic Interactions within the Strong Coupling Regime.

ABSTRACT: We examine the relative magnitudes of electronic coupling HDA in two face-to-face rigid and diastereomeric (porphinato)zinc(II)-quinone (PZn-Q) assemblies, 1β-ZnA and 1β-ZnB, in which the six quinonyl carbon atoms lie in virtually identical arrangements relative to the PZn plane at sub-van der Waals donor-acceptor (D-A) interplanar separations. Steady-state and time-resolved transient optical data and computational studies show that minor differences in relative D-A cofacial orientation give rise to disparate HDA magnitudes for both photoinduced charge separation (CS) and thermal charge recombination (CR). Time-dependent density functional theory (TDDFT) computations illuminate the nature of direct charge transfer states and the electronic structural factors that give rise to these differe

SUBMITTER: Kang YK 

PROVIDER: S-EPMC7687299 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature