A conductive metal-organic framework photoanode.

We report the development of photosensitizing arrays based on conductive metal-organic frameworks (MOFs) that enable light harvesting and efficient charge separation. ZnTTFTB (TTFTB = tetrathiafulvalene tetrabenzoate) MOFs are deposited directly onto TiO photoanodes and structurally characterized by pXRD and EXAFS measurements. Photoinduced interfacial charge transfer dynamics are investigated by combining time-resolved THz spectroscopy and quantum dynamics simulations. Sub-600 fs electron injection into TiO is observed for ZnTTFTB-TiO and is compared to the corresponding dynamics for TTFTB-TiO analogues that lack the extended MOF architecture. Rapid electron injection from the MOF into TiO is enhanced by facile migration of the hole away from the interfacial region. Holes migrate through strongly coupled HOMO orbitals localized on the tetrathiafulvalene cores of the columnar stacks of the MOF, whereas electrons are less easily transferred through the spiral staircase arrangement of phenyl substituents of the MOF. The reported findings suggest that conductive MOFs could be exploited as novel photosensitizing arrays in applications to slow, and thereby make difficult, photocatalytic reactions such as those required for water-splitting in artificial photosynthesis.