Sensitization of TiO2 by Phosphonate-Derivatized Proline Assemblies

Abstract
Surface electrochemical and photoelectrochemical measurements on ITO (In2O3:Sn) or TiO2 of two proline assemblies are reported. Surface coverage on ITO of Pbp-pra(RuIIb2m)-OH(PF6)2 and Bpb-pra(RuIIb2m)-OCH3(CF3CO2)2 are (1.5−2.4) × 10-10 mol/cm2, comparable to monolayer coverages of (1.5−2.5) × 10-10 mol/cm2 for [Ru(bpy)2(4,4‘-(CO2H)2bpy)](PF6)2 and [Ru(bpy)2(4,4‘-(PO3H2)2bpy)](Br)2. Incident photon-to-current conversion efficiency (IPCE) measured in Gräztel-type photovoltaic cells are sensitive to subtle structural differences in the assemblies. IPCE values for Pbp-pra(RuIIb2m)-OH(PF6)2 and Bpb-pra(RuIIb2m)-OCH3(CF3CO2)2 are 2% and 2(4,4‘-(PO3H2)2bpy)](Br)2 and [Ru(bpy)2(4,4‘-(CO2H)2bpy)](PF6)2 under the same conditions.

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