Next to applications in gas storage or drug delivery, metal-organic frameworks (MOFs) also receive increasing attention as redox active catalysts. We have recently reported on a Co-based MOF within the robust and modular MFU-4 structural family that shows promising reversible gas-phase oxidation properties [1]. We here present a density-functional theory (DFT) based computational screening approach to identify other coordinatively unsaturated metal centers or ligands that yield even more redox-active frameworks. A central concern is the accuracy of present-day DFT functionals, and we elucidate systematic shortcomings of semi-local DFT in order to establish it as a reliable and computationally efficient tool for extended in-silico searches. Among the tested ligands hydrides seem particularly promising and we further scrutinize this by detailed mechanistic analysis of potential oxidation reactions.[1] D. Denysenko, T. Werner, M. Grzywa, A. Puls, V. Hagen, G. Eickerling, J. Jelic, K. Reuter, and D. Volkmer, Chem. Commun., 1236 (2012)

DFT study of redox-active metal-organic frameworks

246th National Meeting (2013)

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