Photodriven charge separation in a carotenoporphyrin–quinone triad

Abstract

The key steps in the photosynthetic conversion of light to chemical potential energy include not only photodriven charge separation, but also prevention of the back-reaction (charge recombination). Although the first of these steps has been achieved in several biomimetic solar energy conversion systems, retarding the back-reaction has proved more difficult. This may be accomplished by rapidly moving the electron, the hole, or both away from the site of excitation to more stabilizing environments. In photosynthetic membranes, the electron is transferred sequentially over several closely coupled molecules, including tetrapyrroles and quinones^1–3. In semiconductor/liquid interfacial systems both the electron and the hole migrate following excitation^4,5. We now report that substantial slowing of the back-reaction has been achieved with a tripartite molecule in which a long-lived photodriven charge-separated state of relatively high potential is formed from an excited singlet state in accordance with the above principles. This molecular triad (compound I) consists of a tetraarylporphyrin covalently linked to both a carotenoid and a quinone. In solution, excitation of the porphyrin moiety by visible light results in the rapid (<100 ps) formation of a transient species C^+.−P−Q−^−., with a lifetime on the μs time scale and an energy more than 1 eV above the ground state.