We characterize the electronic rectification properties of molecular linkers that covalently bind Mn catalysts to TiO2 surfaces. We focus on Mn-complexes with phenylterpyridine ligands attached to 3-phenyl-acetylacetonate anchors via amide bonds.1 We find that a suitable choice of the amide linkage yields directionality of interfacial electron transfer, essential to suppress recombination. Our findings are supported by calculations of current-voltage (I-V) characteristics at metallic atomic junctions, based on first-principles methods that combine non-equilibrium Green's function techniques with density functional theory.2,3  Our computational results are consistent with EPR measurements, confirming an asymmetry of electron transfer rates for linkers with significant rectification. The reported studies are particularly relevant for the development of photovoltaic, or photocatalytic, devices based on functionalized TiO2 thin-films where the overall performance is affected by recombination processes competing with interfacial electron injection.McNamara, W. R.; Snoeberger, R. C., III; Li G.; Schleicher, J. M.; Cady, C. W.; Pyatos, M.; Schmuttenmaer, C. A.; Crabtree, R. H.; Brudvig, G. W.; Batista, V. S. J. Am. Chem. Soc. 2008,  130, 14329-14338.Rocha, A. R.; Garcia-Suarez, V.; Bailey, S. W.; Lambert, C. J.; Ferrer, J.; Sanvito, S. Phys. Rev. B 2006,  73, 085414Palma, J. L.; Cao, C.; Zhang, X.-G.; Krstic, P. S.; Krause, J. L.; Cheng, H.-P. J. Phys. Chem. C 2010,  114, 1655-1662.

Diode linkers for the covalent attachment of Mn catalysts to TiO<sub>2</sub> surfaces

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Diode linkers for the covalent attachment of Mn catalysts to TiO2 surfaces

Diode linkers for the covalent attachment of Mn catalysts to TiO₂ surfaces