Tuning Photoinduced Electron Transfer in POM‐Bodipy Hybrids by Controlling the Environment: Experiment and Theory
| Autor: | Pavel Chábera, Albert Masip-Sánchez, Joshua K. G. Karlsson, Sandra Alves, Tõnu Pullerits, Ian P. Clark, Fiona Black, Georgios Toupalas, Sébastien Blanchard, Xavier López, Josep M. Poblet, Youssef Ben M'Barek, Guillaume Izzet, Anna Proust, Elizabeth A. Gibson |
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| Přispěvatelé: | Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Newcastle University [Newcastle], Universitat Rovira i Virgili |
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Materials science 010405 organic chemistry General Chemistry General Medicine 010402 general chemistry 01 natural sciences Catalysis Photoinduced electron transfer Marcus theory 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry chemistry.chemical_compound Molecular dynamics Electron transfer Solvation shell chemistry Chemical physics Intramolecular force Counterion BODIPY [CHIM.OTHE]Chemical Sciences/Other |
| Zdroj: | Angewandte Chemie International Edition Angewandte Chemie International Edition, Wiley-VCH Verlag, In press, ⟨10.1002/anie.202014677⟩ |
| ISSN: | 1521-3757 0044-8249 1433-7851 1521-3773 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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