Membrane-Organized Chemical Photoredox Systems
This project has three interrelated goals relevant to solar water photolysis, which are to develop: (1) vesicle-organized assemblies for H 2 photoproduction that utilize pyrylium and structurally related compounds as combined photosensitizers and cyclic electroneutral transmembrane electron carriers; (2) transmembrane redox systems whose reaction rates can be modulated by light; and (3) homogeneous catalysts for water oxidation. In area (1), initial efforts to photogenerate H 2 from vectorially-organized vesicles containing occluded colloidal Pt and commonly available pyrylium ions as transmembrane redox mediators were unsuccessful. New pyrylium compounds with significantly lower reduction potentials have been synthesized to address this problem, their apparent redox potentials in functioning systems have been now evaluated by using a series of occluded viologens, and H 2 photoproduction has been demonstrated in continuous illumination experiments. In area (2), spirooxazine-quinone dyads have been synthesized and their capacity to function as redox mediators across bilayer membranes has been evaluated through continuous photolysis and transient spectrophotometric measurements. Photoisomerization of the spiro moiety to the ring-open mero form caused net quantum yields to decrease significantly, providing a basis for photoregulation of transmembrane redox. Research on water oxidation (area 3) has been directed at understanding mechanisms of catalysis by cis,cis-[(bpy) 2 Ru(OH 2 )] 2 O 4+ and related polyimine complexes. Using a variety of physical techniques, we have: (i) identified the redox state of the complex ion that is catalytically active; (ii) shown using 18 O isotopic labeling that there are two reaction pathways, both of which involve participation of solvent H 2 O; and (iii) detected and characterized by EPR and resonance Raman spectroscopies new species which may be key intermediates in the catalytic cycle.