Mesoporous thin films comprised of interconnected nanocrystalline (anatase, 20 nm) TiO2 particles were functionalized with [Ru(bpy)(2)(deebq)](PF6)(2), where bpy is 2,2'-bipyridine and deebq is 4,4'-diethylester-2,2'-biquinoline, or iron(III) protoporphyrin IX chloride (hemin). These compounds bind to TiO2 with saturation surface coverages of 8 (+/- 2) x 10(-8) mol/cm(2). Electrochemical measurements show that the compounds first reduction occurs prior to or commensurate with the reduction of the TiO2 electrode. Apparent diffusion constants, D-app, abstracted from chronoabsorption data measured in acetonitrile were found to be dependent on the applied potential and the electrolyte used. The D-app values for reduction of Ru(dcbq)(bpy)(2)/TiO2, where dcbq is 4,4'-(COO-)(2)-2,2'-biquinoline, increased with decreasing surface coverage. At near saturation surface coverage, the apparent diffusion constant was 9.0 x 10(-12) m(2)/s after a potential step from -0.61 to -1.31 vs Fc(+/0). The D-app varied by over a factor of six with applied potential for the oxidation of [Ru(dcbq(-))(bpy)(2)](-)/TiO2 to Ru(dcbq)(bpy)(2)/TiO2. Complete reduction of hemin/TiO2 to heme/TiO2 was observed under conditions where the heme surface coverage was about 1/100 of that expected for monolayer surface coverage. The hemin reduction rates were strongly dependent on the final applied potential. The rates for heme to hemin oxidation were less than or equal to the hemin to heme rates in the presence and absence of pyridine. This behavior was opposite to that observed with Ru(dcbq)(bpy)(2)/TiO2 where reduction was slower than oxidation. A Gerischer-type model was proposed to rationalize the rectifying properties of the interface.