Premium
Tuning Photoinduced Electron Transfer in POM‐Bodipy Hybrids by Controlling the Environment: Experiment and Theory
Author(s) -
Toupalas Georgios,
Karlsson Joshua,
Black Fiona A.,
MasipSánchez 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
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202014677
Subject(s) - counterion , bodipy , chemistry , intramolecular force , photochemistry , marcus theory , chemical physics , electron transfer , photoinduced electron transfer , acceptor , solvation , solvent , solvent effects , ion , computational chemistry , organic chemistry , fluorescence , physics , quantum mechanics , reaction rate constant , kinetics , condensed matter physics
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.