Covalent-Organic Frameworks Composed of Rhenium Bipyridine and Metal Porphyrins: Designing Heterobimetallic Frameworks with Two Distinct Metal Sites

The incorporation of homogeneous catalysts for CO₂ reduction into extended frameworks has been a successful strategy for increasing catalyst lifetime and activity, but the effects of the linkers on catalysis are underexplored. In this work, a novel rhenium bipyridine complex was synthesized for the purpose of designing a covalent-organic framework (COF) with both metalloporphyrin and metal bipyridine moieties. Investigation of the rhenium complex as a homogeneous catalyst shows a faradaic efficiency of 81(8)% for the electrocatalytic conversion of CO₂ to CO upon the addition of methanol as the proton source. Treatment of the rhenium complex with tetra(4-aminophenyl)porphyrin under Schiff base conditions produces the desired COF, as indicated by powder X-ray diffraction (PXRD) studies. Metalation of the porphyrins was accomplished through postsynthetic modification with CoCl₂ and FeCl₃ metal precursors. The retention of the PXRD peaks and appearance of new Co and Fe peaks in the corresponding X-ray photoelectron spectroscopy spectra suggest the successful incorporation of a secondary metal site into the framework. Cyclic voltammetry measurements display increases in current densities when the atmosphere is changed from N₂ to CO₂. Controlled potential electrolyses show that the cobalt-postmetalated COF has the highest activity toward CO₂ reduction, reaching a faradaic efficiency of 18(2)%.