Triarylamine-appended bis(tridentate) cycloruthenated chromophores offer unprecedented control of intramolecular electron transfer at TiO2 surfaces. These dyes have revealed new insights into the undesirable interfacial recombination reaction of the injected electrons with the oxidized compounds, including a significant enhancement of the open circuit photovoltage attributed to a larger surface dipole emanating from translation of the hole away from the interface. Lateral intermolecular hole hopping between dyes can also be observed following visible-light excitation of the amine donor under conditions where the ruthenium(III) centers that reside close to the surface are oxidized. These findings are made possible by transient spectroscopic techniques and careful management of the relative energies of the frontier molecular orbitals within a homologous series of bichromic compounds.

Intramolecular and lateral intermolecular hole transfer at semiconducting surfaces sensitized by bichromic cycloruthenated dyes

248th National Meeting (2014)

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