Photoinduced electron and energy transfer in molecular pentads

• Published in: Journal of the American Chemical Society Vol. 115; no. 24; pp. 11141 - 11152
• Main Authors: Gust, Devens, Moore, Thomas A, Moore, Ana L, Macpherson, Alisdair N, Lopez, Arnaldo, DeGraziano, Janice M, Gouni, Isabelle, Bittersmann, Edith, Seely, Gilbert R
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.12.1993; Amer Chemical Soc
• Subjects: 140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-); 400102 - Chemical & Spectral Procedures; 400500 - Photochemistry; 990200 - Mathematics & Computers; CARBOXYLIC ACIDS; CHEMICAL REACTIONS; Chemistry; Chemistry, Multidisciplinary; COMPLEXES; COMPUTERIZED SIMULATION; ELECTRON TRANSFER; ENERGY TRANSFER; Exact sciences and technology; FLUORESCENCE; GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; General and physical chemistry; HETEROCYCLIC ACIDS; HETEROCYCLIC COMPOUNDS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; LUMINESCENCE; MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; ORGANOMETALLIC COMPOUNDS; PHOTOCHEMICAL REACTIONS; Photochemistry; PHOTOSYNTHESIS; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Physical Sciences; PORPHYRINS; RADICALS; RESONANCE; Science & Technology; SIMULATION; SOLAR ENERGY; SPECTROSCOPY; SYNTHESIS; ZINC COMPLEXES; PHOTOINITIATED CHARGE SEPARATION; SYSTEMS; PORPHYRIN-DIQUINONE TETRAD; QUINONE TRIADS; CAROTENOPORPHYRIN; PHOTOSYNTHESIS; Lifetime; Polyenic compound; Macromolecule; Porphyrin; Quinone; Electron transfer; Photoinduced effect; Organic radical anion; Experimental study; Carotenoid; Energy transfer; Organic radical cation
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00077a011

A series of molecular pentads, each consisting of a porphyrin dyad (P-P) covalently linked to a carotenoid polyene (C) and a diquinone moiety (Q(A)-Q(B)), have been prepared, and the photochemical properties of these molecules have been studied using steady-state and transient absorption and emission spectroscopies. Each of the pentads undergoes photoinduced electron transfer from the C-P-1P-Q(A)-Q(B) singlet state to yield the charge-separated state C-P-P.+-Q(A).--Q(B). Competing with charge recombination of this species are additional electron-transfer reactions operating in series and in parallel which converge on a final C.+-P-P-Q(A)-Q(B).- state. The electron-transfer rate constants and the quantum yields of the various charge-separated species are sensitive functions of the state energies and the electronic coupling between the porphyrin and diquinone moieties. One of the pentads undergoes photoinduced electron transfer to produce the final C.+-P-P-Q(A)-Q(B).- state with a quantum yield of 0.83 and a lifetime of 55 mus. This example of an artificial photosynthetic reaction center preserves about half of the initial excited singlet state energy as chemical potential. Other pentads have charge-separation lifetimes of several hundred microseconds.