Author, as appears in the article.: Toupalas, Georgios; Karlsson, Joshua; Black, Fiona A.; Masip-Sanchez, Albert; Lopez, Xavier; Ben M'Barek, Youssef; Blanchard, Sebastien; Proust, Anna; Alves, Sandra; Chabera, Pavel; Clark, Ian P.; Pullerits, Tonu; Poblet, Josep M.; Gibson, Elizabeth A.; Izzet, Guillaume;
Department: Química Física i Inorgànica
URV's Author/s: López Fernández, Javier / Masip Sánchez, Albert / Poblet Rius, Josep Maria
Keywords: Zinc cytochrome-c Visible-light Redox potentials Polyoxometalates Polyoxometalate Noncovalent interactions Molecular dynamic simulations Kinetics Functionalization Energy Electron transfer Elaboration Donor-acceptor systems Charge-transfer Catalyst dyads
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 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.
Thematic Areas: Química Medicina ii Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: albert.masip@urv.cat albert.masip@urv.cat josepmaria.poblet@urv.cat javier.lopez@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0003-0322-6796
Record's date: 2024-07-27
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202014677
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Angewandte Chemie (International Ed. Print). 60 (12): 6518-6525
APA: Toupalas, Georgios; Karlsson, Joshua; Black, Fiona A.; Masip-Sanchez, Albert; Lopez, Xavier; Ben M'Barek, Youssef; Blanchard, Sebastien; Proust, Anna; (2021). Tuning Photoinduced Electron Transfer in POM-Bodipy Hybrids by Controlling the Environment: Experiment and Theory. Angewandte Chemie (International Ed. Print), 60(12), 6518-6525. DOI: 10.1002/anie.202014677
Article's DOI: 10.1002/anie.202014677
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications
Repositori URV