The ability to control charge migration within porous materials is important for the development of solar photocatalysts and solar energy conversion. Metal organic framework materials are particularly attractive for the development of solar energy applications due to the modularity of design, high porosity, and relative ease of functionalization of these materials. The encapsulation of photoactive guests into porous MOFs is a particularly attractive strategy for the development of photosensitive MOFs since a wide array of light sensitive catalysts have been developed that can be encapsulated within the associated MOF cavities. The Ruthenium polyimine and metalloporphyrins classes of transition metal complexes are particularly attractive for encapsulation into MOFs due to their high stability, ease of functionalization and attractive photophysical properties. Here we report inter-cavity photoinduced electron transfer between co-encapsulated donor-acceptor pairs in two MOF systems (porphyrin donor-accepter complexes and metallo-2,2’-bipyridine donor-accepter complexes in a zinc polyhedral MOF) as well as photo-induced electron transfer between an encapsulated [Ru(II)(2,2’-bipyridine)<sub>3</sub>]<sup>2+</sup> complex and the framework metal cluster in a cobalt(II)-based MOF. The rates of the photoinduced electron transfer are discussed in the framework of Marcus Theory. The results presented here lay the foundation for the future development of robust photocatalytic MOFs for a wide range of solar based energy applications.

Guest-guest and guest-framework photoinduced electron transfer in metal organic frameworks

254th National Meeting (2017)

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