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Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity

[Image: see text] The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems...

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Autores principales: Inan, Damla, Dubey, Rajeev K., Jager, Wolter F., Grozema, Ferdinand C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6344063/
https://www.ncbi.nlm.nih.gov/pubmed/30701014
http://dx.doi.org/10.1021/acs.jpcc.8b08503
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author Inan, Damla
Dubey, Rajeev K.
Jager, Wolter F.
Grozema, Ferdinand C.
author_facet Inan, Damla
Dubey, Rajeev K.
Jager, Wolter F.
Grozema, Ferdinand C.
author_sort Inan, Damla
collection PubMed
description [Image: see text] The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (τ(EET) ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20–2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties.
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spelling pubmed-63440632019-01-28 Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity Inan, Damla Dubey, Rajeev K. Jager, Wolter F. Grozema, Ferdinand C. J Phys Chem C Nanomater Interfaces [Image: see text] The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (τ(EET) ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20–2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties. American Chemical Society 2018-12-18 2019-01-10 /pmc/articles/PMC6344063/ /pubmed/30701014 http://dx.doi.org/10.1021/acs.jpcc.8b08503 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Inan, Damla
Dubey, Rajeev K.
Jager, Wolter F.
Grozema, Ferdinand C.
Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title_full Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title_fullStr Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title_full_unstemmed Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title_short Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity
title_sort tailoring photophysical processes of perylene-based light harvesting antenna systems with molecular structure and solvent polarity
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6344063/
https://www.ncbi.nlm.nih.gov/pubmed/30701014
http://dx.doi.org/10.1021/acs.jpcc.8b08503
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