Alexander U. Czaja

A Metal-Organic Framework with Covalently Bound Organometallic Complexes

A procedure for making covalently linked organometallic complexes within the pores of metal-organic frameworks (MOFs) has been described. An N-heterocyclic carbene precursor containing link L0 was prepared and then constructed into a MOF-5-type structure (IRMOF-76). Attempts to produce covalently bound organometallic complexes in IRMOF-76 were unsuccessful. An alternative way of linking the first metalated link, L1, into the desired metalated MOF structure, IRMOF-77, was successful. IRMOF-76 and -77 were characterized by single-crystal X-ray studies. Demonstration of permanent porosity and successful substitution of the pyridine coligand in IRMOF-77 are also described.

Metal–Organic Frameworks of Vanadium as Catalysts for Conversion of Methane to Acetic Acid

A catalytic system combining the high activity of homogeneous catalysts and the ease of use of heterogeneous catalysts for methane activation is reported. The vanadium-containing metal-organic frameworks (MOFs) MIL-47 and MOF-48 are found to have high catalytic activity and chemical stability. They convert methane selectively to acetic acid with 70% yield (490 TON) based on K(2)S(2)O(8) as an oxidant. Isotopic labeling experiments showed that two methane molecules are converted to the produced acetic acid. The MOF catalysts are reusable and remain catalytically active for several recycling steps without losing their crystalline structures.