Large footprint pyrene chromophores anchored to planar and colloidal metal oxide thin films

Sensitization and binding of a large footprint pyrene chromophore to planar (sapphire) and colloidal metal oxide films (TiO2 and ZrO2) is investigated. The model compound combines a 1-pyrenyl-ethynylenephenylene unit with a new adamantane-tripodal linker that binds to the surface. The linker design, combining a large footprint (approximately 2 nm2) of the tripodal linker with the meta position of the COOH anchoring groups, was suggested from atomistic models, and it aims to provide improved spacing control. The pyrene chromophore unit provides a probe of sensitizer-sensitizer interactions through its propensity to form excimers, unless neighboring pyrene units are sufficiently spaced (>or=3.5 A). Absorption and fluorescence studies, and a comparison with a pyrene-rigid rod model compound, suggest that the new tripodal anchor group allows spacing control on planar surfaces. On colloidal films, the linker provides spacing control at low surface coverage but sensitizer-sensitizer interactions are still observed on colloidal films at high surface coverage. Implications for the functionalization of metal oxide films in hybrid molecule-metal oxide semiconductor material systems are discussed.