title: Electronic coupling effects on photoinduced electron transfer in carotene-porphyrin-fullerene triads detected by time-resolved EPR.
abstract: Photoinduced charge separation and recombination in a carotenoid-porphyrin-fullerene triad C-P-C60 (Bahr et al., 2000) have been followed by time-resolved electron paramagnetic resonance. The electron-transfer process has been characterized in a glass of 2-methyltetrahydrofuran and in the nematic phase of two uniaxial liquid crystals (E-7 and ZLI-1167). In all the different media, the molecular triad undergoes two-step photoinduced electron transfer, with the generation of a long-lived charge-separated state (C*+-P-C60*-), and charge recombination to the triplet state, localized in the carotene moiety, mimicking different aspects of the photosynthetic electron-transfer process. The magnetic interaction parameters have been evaluated by simulation of the spin-polarized radical pair spectrum. The weak exchange interaction parameter (J = +1.7 +/- 0.1 G) provides a direct measure of the dominant electronic coupling matrix element V between the C*+-P-C60*- radical pair state and the recombination triplet state 3C-P-C60. Comparison of the estimated values of V for this triad and a structurally related triad differing only in the porphyrin bridge (octaalkylporphyrin vs tetraarylporphyrin) explains in terms of an electronic coupling effect the approximately 6-fold variation of the recombination rate induced by the modification of the porphyrin bridge as derived by kinetic experiments (Bahr et al., 2000).
authors.affiliation: Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, Italy. marilena.divalentin@unipd.it
authors.forename: Marilena
authors.initials: M
authors.lastname: Di Valentin
authors.forename: Arianna
authors.initials: A
authors.lastname: Bisol
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Agostini
authors.forename: Donatella
authors.initials: D
authors.lastname: Carbonera
mesh_terms: D000465:Algorithms; D002338:Carotenoids / Q000737:chemistry*; D003198:Computer Simulation; D003460:Crystallization; D004578:Electron Spin Resonance Spectroscopy; D004579:Electron Transport; D037741:Fullerenes / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D037741:Fullerenes; D011166:Porphyrins; D002338:Carotenoids