Comments on the through-space singlet energy transfers and energy migration (exciton) in the light harvesting systems.

Recent findings on the photophysical investigations of several cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several serious questions about the mechanism of the energy transfers and energy migration in the light harvesting devices, notably LH II, in the heavily studied purple photosynthetic bacteria. The key issue is that for simple cofacial or slipped dyads with controlled geometry using rigid spacers or spacers with limited flexibilities, the fastest possible rates for singlet energy transfer for three examples are in the 10 x 10(9)s(-1) (i.e. just in the 100 ps time scale) for donor-acceptor distances approaching 3.5-3.6 A. The reported time scale for energy transfers between different bacteriochlorophylls, notably B800*-->B850, is in the picosecond time scale despite the long Mg...Mg separation of approximately 18 A. Such a short rate drastically contrasts with the well accepted Förster theory. This article reviews the modern knowledge of the structure, bacteriochlorophyll a transition moments, and photophysical processes and dynamics in LH II, and compares these parameters with the recently investigated model bisporphyrin dyads build upon octa-etio-porphyrin chromophores and rigid and semi-rigid spacers. The recently discovered role of the rhodopin glucoside residue called carotenoid will be commented as the possible relay for energy transfer, including the possibility of uphill processes at room temperature. In this context, the concept of energy migration, called exciton, may also be affected by relays and uphill processes. Also, it is becoming more and more apparent that the presence of an irreversible electron transfer reaction at the reaction center, i.e. electron transfer from the special pair to the phyophytin macrocycle and so on, renders the rates for energy transfer and migration more rapid precluding all possibility of back transfers.