Metal organic framework (MOF) materials are attractive candidates 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 class of transition metal complex is attractive for encapsulation into MOFs due to their high stability, ease of functionalization and attractive photophysical properties. We have previously demonstrated significant effects on the photophysics of [Ru(2,2’-bipyridine)3]2+ (RuBpy) through encapsulation within various Zn2+ based MOFs including extended 3MLCT lifetimes and shifted absorption and emission spectra. Here we utilize time dependent density functional theory to obtain a molecularly detailed understanding of the effects of RuBpy encapsulation in the MOF RWLC-5. This Cd-carboxylate MOF exhibits exceptional stability and enhanced photophysics. The high resolution of the crystal structure reveals a distorted RuBpy cation which contributes to the altered photophysics as revealed by TDDFT. In addition, TDDFT further reveals that non-covalent interactions between the RuBpy and the framework components also effect the excited state dynamics. Overall, the results presented here lay the foundation for the future development of robust photocatalytic MOFs for a wide range of solar based energy applications.

Modulating the photophysics of ruthenium polyimine complexes through encapsulation in metal organic frameworks: A time dependent density functional theory study

256th National Meeting (2018)

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