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Title: Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C 60 : Synthesis, Supramolecular Formation and Excited-State Processes

Abstract

Simultaneous occurrence of energy and electron transfer events involving different acceptor sites in a newly assembled supramolecular triad comprised of covalently linked free-base porphyrin–zinc porphyrin dyad, H2P-ZnP axially coordinated to electron acceptor fullerene, has been successfully demonstrated. The dyad was connected through the β-pyrrole positions of the porphyrin macrocycle instead of the traditionally used meso-positions for better electronic communication. Interestingly, the β-pyrrole functionalization modulated the optical properties to such an extent that it was possible to almost exclusively excite the zinc porphyrin entity in the supramolecular triad. The measured binding constant for the complex with 1:1 molecular stoichiometry was in the order of 104 m-1 revealing moderately stable complex formation. An energy level diagram constructed using optical, electrochemical and computational results suggested that both the anticipated energy and electron events are thermodynamically feasible in the triad. Consequently, it was possible to demonstrate occurrence of excited state energy transfer to the covalently linked H2P, and electron transfer to the coordinated ImC60 from studies involving steady-state and time-resolved emission, and femto- and nanosecond transient absorption studies. The estimated energy transfer was around 67 % in the dyad with a rate constant of 1.1×109 s-1. In the supramolecular triad, the charge separated statemore » was rather long-lived although it was difficult to arrive the exact lifetime of charge separated state from nanosecond transient spectral studies due to overlap of strong triplet excited signals of porphyrin in the monitoring wavelength window. Nevertheless, simultaneous occurrence of energy and electron transfer in the appropriately positioned energy and electron acceptor entities in a supramolecular triad was possible to demonstrate in the present study, a step forward to unraveling the complex photochemical events occurring in natural photosynthesis and its implications in building light energy harvesting devices.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of North Texas, Denton, TX (United States)
Publication Date:
Research Org.:
Miami Univ., Oxford, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1533141
Alternate Identifier(s):
OSTI ID: 1392178
Grant/Contract Number:  
SC0010800; FG02-13ER46976
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 52; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Hu, Yi, Thomas, Michael B., Jinadasa, R. G. Waruna, Wang, Hong, and D'Souza, Francis. Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C 60 : Synthesis, Supramolecular Formation and Excited-State Processes. United States: N. p., 2017. Web. https://doi.org/10.1002/chem.201702178.
Hu, Yi, Thomas, Michael B., Jinadasa, R. G. Waruna, Wang, Hong, & D'Souza, Francis. Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C 60 : Synthesis, Supramolecular Formation and Excited-State Processes. United States. https://doi.org/10.1002/chem.201702178
Hu, Yi, Thomas, Michael B., Jinadasa, R. G. Waruna, Wang, Hong, and D'Souza, Francis. Wed . "Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C 60 : Synthesis, Supramolecular Formation and Excited-State Processes". United States. https://doi.org/10.1002/chem.201702178. https://www.osti.gov/servlets/purl/1533141.
@article{osti_1533141,
title = {Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C 60 : Synthesis, Supramolecular Formation and Excited-State Processes},
author = {Hu, Yi and Thomas, Michael B. and Jinadasa, R. G. Waruna and Wang, Hong and D'Souza, Francis},
abstractNote = {Simultaneous occurrence of energy and electron transfer events involving different acceptor sites in a newly assembled supramolecular triad comprised of covalently linked free-base porphyrin–zinc porphyrin dyad, H2P-ZnP axially coordinated to electron acceptor fullerene, has been successfully demonstrated. The dyad was connected through the β-pyrrole positions of the porphyrin macrocycle instead of the traditionally used meso-positions for better electronic communication. Interestingly, the β-pyrrole functionalization modulated the optical properties to such an extent that it was possible to almost exclusively excite the zinc porphyrin entity in the supramolecular triad. The measured binding constant for the complex with 1:1 molecular stoichiometry was in the order of 104 m-1 revealing moderately stable complex formation. An energy level diagram constructed using optical, electrochemical and computational results suggested that both the anticipated energy and electron events are thermodynamically feasible in the triad. Consequently, it was possible to demonstrate occurrence of excited state energy transfer to the covalently linked H2P, and electron transfer to the coordinated ImC60 from studies involving steady-state and time-resolved emission, and femto- and nanosecond transient absorption studies. The estimated energy transfer was around 67 % in the dyad with a rate constant of 1.1×109 s-1. In the supramolecular triad, the charge separated state was rather long-lived although it was difficult to arrive the exact lifetime of charge separated state from nanosecond transient spectral studies due to overlap of strong triplet excited signals of porphyrin in the monitoring wavelength window. Nevertheless, simultaneous occurrence of energy and electron transfer in the appropriately positioned energy and electron acceptor entities in a supramolecular triad was possible to demonstrate in the present study, a step forward to unraveling the complex photochemical events occurring in natural photosynthesis and its implications in building light energy harvesting devices.},
doi = {10.1002/chem.201702178},
journal = {Chemistry - A European Journal},
number = 52,
volume = 23,
place = {United States},
year = {2017},
month = {6}
}

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