High-Throughput Microscale MOF Catalysis via Solid Dispersion Reactor Dosing.

Metal-organic frameworks (MOFs) exhibit exceptional structural diversity and tunable chemical environments, offering excellent opportunities for tuning the selectivity of catalytic centers confined to their pores. As such, MOF catalysts have been shown to exhibit distinct size-, regio-, and chemoselectivity relative to those of other heterogeneous platforms. Despite these advantages, the discovery and optimization of highly active and selective MOF catalysts for complex transformations remain challenging. Their poor solubility, low bulk density, and mechanical fragility complicate their integration into small-scale, high-throughput (HT) experiments that would otherwise facilitate catalyst optimization. In this work, we present the adaptation of inexpensive bead-based reactor dosing methodologies to overcome these limitations. A central feature of this strategy is the development of plate-reader-based analysis of reactor dosing, which enables the rapid optimization of MOF-bead formulations for accurate and precise well-to-well dosing. The utility of this approach is demonstrated in a proof-of-concept study involving the identification and optimization of a novel MOF-catalyzed C-H oxidation reaction, thereby establishing an accessible workflow for accelerating the development of MOF catalysts in batch reaction formats.