Synthetic Control of Exciton Dynamics in Bioinspired Cofacial Porphyrin Dimers

Partha Pratim Roy, Sohang Kundu, Jesus Valdiviezo, George Bullard, James T. Fletcher, Rui Liu, Shiun Jr Yang, Peng Zhang, David N. Beratan, Michael J. Therien, Nancy Makri, Graham R. Fleming

Research output: Contribution to journalArticlepeer-review


Understanding how the complex interplay among excitonic interactions, vibronic couplings, and reorganization energy determines coherence-enabled transport mechanisms is a grand challenge with both foundational implications and potential payoffs for energy science. We use a combined experimental and theoretical approach to show how a modest change in structure may be used to modify the exciton delocalization, tune electronic and vibrational coherences, and alter the mechanism of exciton transfer in covalently linked cofacial Zn-porphyrin dimers (meso-beta linked ABm-βand meso-meso linked AAm-m). While both ABm-βand AAm-mfeature zinc porphyrins linked by a 1,2-phenylene bridge, differences in the interporphyrin connectivity set the lateral shift between macrocycles, reducing electronic coupling in ABm-βand resulting in a localized exciton. Pump-probe experiments show that the exciton dynamics is faster by almost an order of magnitude in the strongly coupled AAm-mdimer, and two-dimensional electronic spectroscopy (2DES) identifies a vibronic coherence that is absent in ABm-β. Theoretical studies indicate how the interchromophore interactions in these structures, and their system-bath couplings, influence excitonic delocalization and vibronic coherence-enabled rapid exciton transport dynamics. Real-time path integral calculations reproduce the exciton transfer kinetics observed experimentally and find that the linking-modulated exciton delocalization strongly enhances the contribution of vibronic coherences to the exciton transfer mechanism, and that this coherence accelerates the exciton transfer dynamics. These benchmark molecular design, 2DES, and theoretical studies provide a foundation for directed explorations of nonclassical effects on exciton dynamics in multiporphyrin assemblies.

Original languageEnglish (US)
Pages (from-to)6298-6310
Number of pages13
JournalJournal of the American Chemical Society
Issue number14
StatePublished - Apr 13 2022

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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