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Dissecting the Nature of Exciton Interactions in Ethyne-Linked Tetraarylporphyrin Arrays

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Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Risorgimento 35, 56126 Pisa, Italy
Departament de Fisicoquímica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII s/n, 08028 Barcelona, Spain
Cite this: J. Phys. Chem. C 2013, 117, 24, 12423–12431
Publication Date (Web):April 16, 2013
https://doi.org/10.1021/jp4020433
Copyright © 2013 American Chemical Society

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    Abstract

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    We investigate how electronic energy transfer in a series of three ethyne-linked zinc- and free base tetraarylporphyrin dimers is tuned by the type of linker and by substitution on the porphyrin rings. We use time-dependent density functional theory (TD-DFT) combined with a recently developed fully polarizable QM/MM/PCM method. This allows us to dissect the bridge-mediated contributions to energy transfer in terms of superexchange (through-bond) interactions and Coulomb (through-space) terms mediated by the polarizability of the bridge. We explore the effects of the substituents and of the bridge-chromophore mutual orientation on these contributions. We find that bridge-mediated superexchange contributions largely boost energy transfer between the porphyrin units. When the effect of the solvent is also considered through the polarizable continuum model (PCM), we find good agreement with the through-bond versus through-space contributions determined experimentally, thus indicating the need to properly include both solvent and bridge effects in the study of energy transfer in bridged molecular dyads.

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    Cited By

    This article is cited by 6 publications.

    1. Stefano Caprasecca and Benedetta Mennucci . Excitation Energy Transfer in Donor-Bridge-Acceptor Systems: A Combined Quantum-Mechanical/Classical Analysis of the Role of the Bridge and the Solvent. The Journal of Physical Chemistry A 2014, 118 (33) , 6484-6491. https://doi.org/10.1021/jp502815r
    2. Stefano Caprasecca, Sandro Jurinovich, Lucas Viani, Carles Curutchet, and Benedetta Mennucci . Geometry Optimization in Polarizable QM/MM Models: The Induced Dipole Formulation. Journal of Chemical Theory and Computation 2014, 10 (4) , 1588-1598. https://doi.org/10.1021/ct500021d
    3. Hasini Medagedara, Mandefro Y. Teferi, Sachithra T. Wanasinghe, Wade Burson, Shahad Kizi, Bradly Zaslona, Kristy L. Mardis, Jens Niklas, Oleg G. Poluektov, Aaron S. Rury. Decorrelated singlet and triplet exciton delocalization in acetylene-bridged Zn-porphyrin dimers. Chemical Science 2024, 15 (5) , 1736-1751. https://doi.org/10.1039/D3SC03327A
    4. Lorenzo Cupellini, Samuele Giannini, Benedetta Mennucci. Electron and excitation energy transfers in covalently linked donor–acceptor dyads: mechanisms and dynamics revealed using quantum chemistry. Physical Chemistry Chemical Physics 2018, 20 (1) , 395-403. https://doi.org/10.1039/C7CP07002K
    5. Daniele Varsano, Stefano Caprasecca, Emanuele Coccia. Theoretical description of protein field effects on electronic excitations of biological chromophores. Journal of Physics: Condensed Matter 2017, 29 (1) , 013002. https://doi.org/10.1088/0953-8984/29/1/013002
    6. Arnaud Fihey, Roberto Russo, Lorenzo Cupellini, Denis Jacquemin, Benedetta Mennucci. Is energy transfer limiting multiphotochromism? answers from ab initio quantifications. Physical Chemistry Chemical Physics 2017, 19 (3) , 2044-2052. https://doi.org/10.1039/C6CP07458H

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