2020/11/30 by Duvalier Madrid-Úsuga, John H. Reina
Chemistry · Engineering · Neuroscience · Physics and Astronomy · #Acceptor #BODIPY #Chemical physics #Chemistry #Electron transfer #Fluorescence #HOMO/LUMO #Materials science #Molecular Junctions and Nanostructures #Molecule #Organic chemistry #Photochemistry #Photoinduced electron transfer #Photoreceptor and optogenetics research #Physics #Spectroscopy #Spectroscopy and Quantum Chemical Studies #Ultrafast laser spectroscopy #physics.chem-ph
paper · pdf · doi:10.1021/acs.jpca.1c00603
14 pages, 12 figures
arxiv created 2021/03/11 · openalex publication_date 2021/03/23 · arxiv updated 2021/06/09 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Photoinduced electron transfer in multichromophore molecular systems is defined by a critical interplay between their core unit configuration (donor, molecular bridge, and acceptor) and their system–solvent coupling; these lead to energy and charge transport processes that are key in the design of molecular antennas for efficient light harvesting and organic photovoltaics. Here, we quantify the ultrafast non-Markovian dissipative dynamics of electron transfer in D−π–A molecular photosystems comprising 1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (BODIPY), Zn–porphyrin, fulleropyrrolidine, and fulleroisoxazoline. We find that the stabilization energy of the charge transfer states exhibits a significant variation for different polar (methanol, tetrahydrofuran (THF)) and nonpolar (toluene) environments and determine such sensitivity according to the molecular structure and the electron–vibration couplings that arise at room temperature. For the considered donor–acceptor (D–A) dyads, we show that the stronger the molecule–solvent coupling, the larger the electron transfer rates, regardless of the dyads’ electronic coherence properties. We find such coupling strengths to be the largest (lowest) for methanol (toluene), with an electron transfer rate difference of 2 orders of magnitude between the polar and nonpolar solvents. For the considered donor–bridge–acceptor (D–B–A) triads, the molecular bridge introduces an intermediate state that allows the realization of Λ or cascaded-type energy mechanisms. We show that the latter configuration, obtained for BDP-ZnP-[PyrC 60 ] in methanol, exhibits the highest transfer rate of all of the computed triads. Remarkably, and in contrast with the dyads, we show that the larger charge transfer rates are obtained for triads that exhibit prolonged electron coherence and population oscillations.