Two artificial photosynthetic reaction centers consisting of a porphyrin (P) covalently linked to both a carotenoid polyene (C) and a fullerene derivative (C60) have been prepared and found to transfer triplet excitation energy from the fullerene moiety of C-P-3C60 to the carotenoid polyene, yielding 3C-P-C60. The transfer has been studied both in toluene at ambient temperatures and in 2-methyltetrahydrofuran at lower temperatures. The energy transfer is an activated process, with E(a) = 0.17 eV. This is consistent with transfer by a triplet energy transfer relay, whereby energy first migrates from C-P-3C60 to the porphyrin, yielding C-3P-C60 in a slow, thermally activated step. Rapid energy transfer from the porphyrin triplet to the carotenoid gives the final state. Triplet relays of this sort have been observed in photosynthetic reaction centers, and are part of the system that protects the organism from damage by singlet oxygen, whose production is sensitized by chlorophyll triplet states. The fullerene-containing triads can also demonstrate stepwise photoinduced electron transfer to yield long-lived C.+-P-C60.- charge-separated states. Electron transfer occurs even at 8 K. Charge recombination of C.+-P-C60.- yields 3C-P-C60, rather than the molecular ground state. These photochemical events are reminiscent of photoinduced electron transfer in photosynthetic reaction centers.
|Number of pages||8|
|Journal||Journal of Photochemistry and Photobiology B: Biology|
|Publication status||Published - Jun 1 1998|
- Energy transfer
ASJC Scopus subject areas
- Plant Science
- Physical and Theoretical Chemistry