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Metal ion-linked multilayers offer an easily prepared and modular architecture for controlling energy and electron transfer events on nanoparticle, metal oxide films. However, unlike with planar electrodes, the mesoporous nature of the films inherently limits both the thickness of the multilayer and subsequent diffusion through the pores. Here, we systematically investigated the role of TiO 2 nanoparticle film porosity and metal ion-linked multilayer thickness in surface loading, through-pore diffusion, and overall device performance. The TiO 2 porosity was controlled by varying TiO 2 sintering times. Molecular multilayer thickness was controlled through assembling Zn II -linked bridging molecules (B = p-terphenyl diphosphonic acid) between the metal oxide and the Ru(bpy) 2 ((4,4′-PO 3 H 2 ) 2 bpy)]Cl 2 dye (RuP), thus producing TiO 2 -(B n )-RuP films. Using attenuated total reflectance infrared absorption and UV−vis spectroscopy, we observed that at least two molecular layers (i.e., TiO 2 -B 2 or TiO 2 -B 1 -RuP) could be formed on all films but subsequent loading was dependent on the porosity of the TiO 2 . Rough estimates indicate that in a film with 34 nm average pore diameter, the maximum multilayer film thickness is on the order of 4.6−6 nm, which decreases with decreasing pore size. These films were then incorporated as the photoanodes in dye-sensitized solar cells with cobalt(II/III)tris(4,4′-di-tert-butyl-2,2′-bipyridine) as a redox mediator. In agreement with the surface-loading studies, electrochemical impedance spectroscopy measurements indicate that mediator diffusion is significantly hindered in films with thicker multilayers and less porous TiO 2 . Collectively, these results show that care must be taken to balance multilayer thickness, substrate porosity, and size of the mediator in designing and maximizing the performance of new multilayer energy and electron management architectures.

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