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

Journal Article (Journal Article)

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 differential HDAs. These data show more extensive mixing of locally excited (LE) and CS states in 1β-ZnA relative to 1β-ZnB and that these HDA differences track the magnitudes of electronic coupling matrix elements determined from steady-state electronic spectral data and thermal CR rate constants measured via pump-probe spectroscopy. Collectively, this work shows that electron transfer dynamics may be manipulated in cofacial D-A systems, even at sub-van der Waals contact, provided that conformational rigidity precludes structural fluctuations that modulate D-A interactions on the charge transfer time scale.

Full Text

Duke Authors

Cited Authors

  • Kang, YK; Zhang, P; Rubtsov, IV; Zheng, J; Bullard, G; Beratan, DN; Therien, MJ

Published Date

  • December 2, 2019

Published In

Volume / Issue

  • 123 / 49

Start / End Page

  • 10456 - 10462

PubMed ID

  • 31710233

Pubmed Central ID

  • 31710233

Electronic International Standard Serial Number (EISSN)

  • 1520-5207

International Standard Serial Number (ISSN)

  • 1520-6106

Digital Object Identifier (DOI)

  • 10.1021/acs.jpcb.9b07627


  • eng