Chemical Approaches to Artificial Photosynthesis. 2

Inorg Chem. 2005 Oct 3;44(20):6802-27. doi: 10.1021/ic050904r.


The goal of artificial photosynthesis is to use the energy of the sun to make high-energy chemicals for energy production. One approach, described here, is to use light absorption and excited-state electron transfer to create oxidative and reductive equivalents for driving relevant fuel-forming half-reactions such as the oxidation of water to O2 and its reduction to H2. In this "integrated modular assembly" approach, separate components for light absorption, energy transfer, and long-range electron transfer by use of free-energy gradients are integrated with oxidative and reductive catalysts into single molecular assemblies or on separate electrodes in photelectrochemical cells. Derivatized porphyrins and metalloporphyrins and metal polypyridyl complexes have been most commonly used in these assemblies, with the latter the focus of the current account. The underlying physical principles--light absorption, energy transfer, radiative and nonradiative excited-state decay, electron transfer, proton-coupled electron transfer, and catalysis--are outlined with an eye toward their roles in molecular assemblies for energy conversion. Synthetic approaches based on sequential covalent bond formation, derivatization of preformed polymers, and stepwise polypeptide synthesis have been used to prepare molecular assemblies. A higher level hierarchial "assembly of assemblies" strategy is required for a working device, and progress has been made for metal polypyridyl complex assemblies based on sol-gels, electropolymerized thin films, and chemical adsorption to thin films of metal oxide nanoparticles.