Energy transfer and spin polarization of the carotenoid triplet state in synthetic carotenoporphyrin dyads and in natural antenna complexes

A series of carotenoporphyrin dyads, in which the carotenoid is covalently linked to a tetraarylporphyrin at the ortho, meta or para position of one of the meso aromatic rings, has been studied using Time-Resolved Electron Paramagnetic Resonance (TREPR) spectroscopy. In parallel, an investigation has been carried, on two different photosynthetic antenna systems, the B800-B850 complex of R, acidophila and the LHCII complex of higher organisms. The initial spin polarization of the carotenoid triplet-state, populated indirectly by laser excitation, has been detected. It has been demonstrated that the initial polarization is not a characteristic property of the carotenoid triplet-state, as previously stated, but depends on the donor-acceptor mutual orientation. The triplet energy transfer to the carotenoid from a chlorophyll or porphyrin triplet state is discussed on the basis of the observed spin polarization.