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We report our investigation into the MCU-inhibitory activity of Co3+ complexes in comparison to Ru265. These compounds reversibly inhibit the MCU with nanomolar potency. Mutagenesis studies and molecular docking simulations suggest that the complexes operate through interactions with the DIME motif of the MCU pore.Diversity-oriented synthesis of energetic pyrimidine structures with geminal explosophoric groups of geminal dinitro and azido-nitro groups via a novel reductive cleavage and oxidative coupling strategy is reported. Fluorine ha