Through space singlet energy transfers in light-harvesting systems and cofacial bisporphyrin dyads

Abstract

Recent discoveries from our research groups on the photophysics of a few cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several important investigations about the mechanism of energy transfers and energy migration in light-harvesting devices, notably LH II, in the heavily investigated purple photosynthetic bacteria. The key feature is that for face-to-face and slipped dyads with controlled structure using rigid spacers or spacers with limited flexibilities, our fastest rates for singlet energy transfer are in the 10 × 109 s -1 (i.e. 100 ps time scale) for donor-acceptor distances of ~3.5–3.6 Å. The time scale for energy transfers between different bacteriochlorophylls, notably B800*→B850, is in the ps despite the long Mg ⋯ Mg separation (~18 Å). This short rate drastically contrasts with the well-accepted Förster theory. This review focuses on the photophysical processes and dynamics in LH II and compares these parameters with our investigated model dyads build upon octa-etio-porphyrin chromophores and rigid and semi-rigid spacers. The recently discovered role of the rhodopin glucoside (carotenoid) will be analyzed as possible relay for energy transfers, including the possibility of uphill processes at room temperature. In this context the concept of energy migration may be complemented by parallel relays and uphill processes. It is also becoming more obvious that the irreversible electron transfer at the reaction center (electron transfer from the special pair to the phaeophytin) renders the rates for energy transfer and migration faster precluding all possibility of back transfers.