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

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 i...

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Veröffentlicht in:Angewandte Chemie International Edition Jg. 60; H. 12; S. 6518 - 6525
Hauptverfasser: Toupalas, Georgios, Karlsson, Joshua, Black, Fiona A., Masip‐Sánchez, Albert, López, Xavier, Ben M'Barek, Youssef, Blanchard, Sébastien, Proust, Anna, Alves, Sandra, Chabera, Pavel, Clark, Ian P., Pullerits, Tönu, Poblet, Josep M., Gibson, Elizabeth A., Izzet, Guillaume
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Germany Wiley Subscription Services, Inc 15.03.2021
Wiley-VCH Verlag
Ausgabe:International ed. in English
Schlagworte:
Boron
Charge transfer
Chemical Sciences
Condensed Matter Physics (including Material Physics, Nano Physics)
Den kondenserade materiens fysik (Här ingår: Materialfysik, nanofysik)
donor-acceptor systems
Electrochemical analysis
Electrochemistry
Electron transfer
Electrons
Energy charge
Fysik
Fysikalisk kemi (Här ingår: Yt- och kolloidkemi)
Hybrids
Kemi
Materialkemi
Materials Chemistry
molecular dynamic simulations
Molecular dynamics
Natural Sciences
Naturvetenskap
noncovalent interactions
Optical properties
or physical chemistry
Other
Physical Chemistry (including Surface- and Colloid Chemistry)
Physical Sciences
polyoxometalates
Polyoxometallates
Recombination
Solvation
Solvents
Theoretical and
donor-acceptor systems
molecular dynamic simulations
electron transfer
noncovalent interactions
polyoxometalates
ISSN:1433-7851, 1521-3773, 1521-3773
Online-Zugang:Volltext
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Zusammenfassung: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. The intramolecular photoinduced electron transfer of a series of polyoxometalate (POM)‐bodipy hybrids was examined. The data show that both solvents and counterions have a major impact on the relaxation dynamics of the excited states by modifying the solvation shell around the POM. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods.
Bibliographie:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202014677