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-[PyrC60] 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.