title: Zeolite-like metal-organic frameworks as platforms for applications: on metalloporphyrin-based catalysts.
abstract: The extra-large cavities of zeolite-like metal-organic frameworks (ZMOFs) offer great potential for their exploration in applications pertinent to larger molecules, like porphyrins. The anionic nature of the framework allowed for facile in situ encapsulation of a cationic free-base porphyrin, and the alpha-cage of our (In-imidazoledicarboxylate)-based rho-ZMOF is ideally suited to the isolation of one porphyrin molecule per cage, which prevents the oxidative self-degradation associated with self-dimerization common in homogeneous catalysis and upon aggregation in solid supports like mesoporous silicates or polymers. The encapsulation of a free-base porphyrin [5,10,15,20-tetrakis(1-methyl-4- pyridinio)porphyrin] and the stability of the rho-ZMOF to metalation conditions, allows for the preparation of a variety of metalloporphyrins (i.e., Mn, Cu, Co, Zn ions) with the ZMOF serving as a platform. The Mn-metallated porphyrin encapsulated in rho-ZMOF shows catalytic activity toward the oxidation of cyclohexane, with turn-over numbers, to the best of our knowledge, higher than reported for similar heterogeneous systems, and our system can be recycled up to 11 cycles, which represents a longer lifetime than reported for any other system.
authors.affiliation: Department of Chemistry, University of South Florida, 4202 East Fowler Avenue (CHE205), Tampa, Florida 33620, USA.
authors.forename: Mohamed H
authors.initials: MH
authors.lastname: Alkordi
authors.forename: Yunling
authors.initials: Y
authors.lastname: Liu
authors.forename: Randy W
authors.initials: RW
authors.lastname: Larsen
authors.forename: Jarrod F
authors.initials: JF
authors.lastname: Eubank
authors.forename: Mohamed
authors.initials: M
authors.lastname: Eddaoudi