Sorption and catalysis by robust microporous metalloporphyrin framework solids

Two isostructural metalloporphyrin framework solids have been synthesized. Both frameworks contains manganese(III) metal complexes of trans-dicarboxylateporphyrins whose peripheralcarboxylates coordinate the edges of tetrahedral Zn4O+6 clusters; the two metalloporphyrins explored are Mn(III) and Co(II). The cubic interpenetrated frameworks have 72% free volume and 4 x 7 angstrom averaged size pores. The evacuated frameworks are robust and retain a structure open to the sorption of substrates with medium polarity. The manganese porphyrin framework catalyzes the hydroxylation of cyclic and linear alkanes with iodosylbenzene as oxidant in a size-and polarity-selective manner. In addition, the catalysis was found to occur within the pores, making this a rare case of porphyrin framework solid with interior catalysis.