Photoexcited Energy Relaxation in Porphyrin Nanorings

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Author(s)Rueda Espinosa, Kennet J.
Author(s)Kananenka, Alexei A.
Date Accessioned2024-10-16T16:43:14Z
Date Available2024-10-16T16:43:14Z
Publication Date2024-08-19
DescriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.4c03849. This article will be embargoed until 08/19/2025.
AbstractNatural photosynthetic systems convert solar energy to chemical energy with an extremely high efficiency. Synthetic chromophore arrays are promising models for understanding and mimicking energy migration in natural light-harvesting systems. To duplicate the structure and function of natural systems, a multitude of cyclic porphyrin arrays have been synthesized over the past several decades. In a recent breakthrough [Nat. Chem. 2022, 14, 1436–1442], synthetic butadiyne-linked porphyrin nanorings have been shown to exhibit excitation energy transfer on the same timescale and length scale as the natural light-harvesting complex LH2 and with comparable efficiency. In the pursuit of understanding the fundamental underpinnings of the exciton dynamics in such systems, we combined time-dependent density functional theory with the hierarchical equation of motion approach and performed a systematic study of population dynamics, coherence length, and the energy transfer in linear and cyclic multiporphyrin nanostructures with and without the butadiyne moiety. In very good agreement with experiments, we showed that the ultrafast delocalization process of the exciton in symmetric structures occurs during the first 300 fs after the excitation. Migration and localization of the excitation in segments with π-conjugation links happen on a timescale of tens of picoseconds. We also found that coherence length dynamics in multiporphyrin systems are very robust to the environmental effects. Another notable feature of butadiyne-linked porphyrin nanorings is that their energy transfer efficiency can exceed 80%.
SponsorThis work is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award number DE-SC0024511. A.A.K. also acknowledges the start-up funds provided by the College of Arts and Sciences and the Department of Physics and Astronomy of the University of Delaware. Calculations were performed with high-performance computing resources provided by the University of Delaware.
CitationRueda Espinosa, Kennet J., and Alexei A. Kananenka. “Photoexcited Energy Relaxation in Porphyrin Nanorings.” The Journal of Physical Chemistry C 128, no. 34 (August 29, 2024): 14347–56. https://doi.org/10.1021/acs.jpcc.4c03849.
ISSN1932-7455
URLhttps://udspace.udel.edu/handle/19716/35235
Languageen_US
PublisherJournal of Physical Chemistry C
Keywordsdelocalization
Keywordsenergy
Keywordsexcitons
Keywordsoligomers
Keywordspyrroles
TitlePhotoexcited Energy Relaxation in Porphyrin Nanorings
TypeArticle
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