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Tuning Photoinduced Electron Transfer in POM-Bodipy Hybrids by Controlling the Environment : Experiment and Theory

Toupalas, Georgios ; Karlsson, Joshua ; Black, Fiona A. ; Masip-Sánchez, Albert ; López, Xavier ; Ben M'Barek, Youssef ; Blanchard, Sébastien ; Proust, Anna ; Alves, Sandra and Chabera, Pavel LU , et al. (2021) In Angewandte Chemie - International Edition 60(12). p.6518-6525
Abstract

The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron-dipyrromethene) light-harvesting units were examined. Evaluated here in this polyanionic donor-acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The results show that both solvents and counterions have a major impact upon the energy of the charge-transfer state by modifying the solvation shell around the POMs. This modification leads to a significantly shorter charge separation time in the case of smaller counterion and slower charge recombination in a less polar solvent. These results were rationalized in terms of Marcus theory and show... (More)

The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron-dipyrromethene) light-harvesting units were examined. Evaluated here in this polyanionic donor-acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The results show that both solvents and counterions have a major impact upon the energy of the charge-transfer state by modifying the solvation shell around the POMs. This modification leads to a significantly shorter charge separation time in the case of smaller counterion and slower charge recombination in a less polar solvent. These results were rationalized in terms of Marcus theory and show that solvent and counterion both affect the driving force for photoinduced electron transfer and the reorganization energy. This was corroborated with theoretical investigations combining DFT and molecular dynamics simulations.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
donor-acceptor systems, electron transfer, molecular dynamic simulations, noncovalent interactions, polyoxometalates
in
Angewandte Chemie - International Edition
volume
60
issue
12
pages
6518 - 6525
publisher
John Wiley & Sons Inc.
external identifiers
  • pmid:33350554
  • scopus:85100708798
ISSN
1433-7851
DOI
10.1002/anie.202014677
language
English
LU publication?
yes
id
363d86d0-71b2-4221-8ff4-147c33175b9e
date added to LUP
2021-03-05 12:34:05
date last changed
2025-07-11 21:09:47
@article{363d86d0-71b2-4221-8ff4-147c33175b9e,
  abstract     = {{<p>The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron-dipyrromethene) light-harvesting units were examined. Evaluated here in this polyanionic donor-acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The results show that both solvents and counterions have a major impact upon the energy of the charge-transfer state by modifying the solvation shell around the POMs. This modification leads to a significantly shorter charge separation time in the case of smaller counterion and slower charge recombination in a less polar solvent. These results were rationalized in terms of Marcus theory and show that solvent and counterion both affect the driving force for photoinduced electron transfer and the reorganization energy. This was corroborated with theoretical investigations combining DFT and molecular dynamics simulations.</p>}},
  author       = {{Toupalas, Georgios and Karlsson, Joshua and Black, Fiona A. and Masip-Sánchez, Albert and López, Xavier and Ben M'Barek, Youssef and Blanchard, Sébastien and Proust, Anna and Alves, Sandra and Chabera, Pavel and Clark, Ian P. and Pullerits, Tönu and Poblet, Josep M. and Gibson, Elizabeth A. and Izzet, Guillaume}},
  issn         = {{1433-7851}},
  keywords     = {{donor-acceptor systems; electron transfer; molecular dynamic simulations; noncovalent interactions; polyoxometalates}},
  language     = {{eng}},
  number       = {{12}},
  pages        = {{6518--6525}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Angewandte Chemie - International Edition}},
  title        = {{Tuning Photoinduced Electron Transfer in POM-Bodipy Hybrids by Controlling the Environment : Experiment and Theory}},
  url          = {{http://dx.doi.org/10.1002/anie.202014677}},
  doi          = {{10.1002/anie.202014677}},
  volume       = {{60}},
  year         = {{2021}},
}