Chemical Fixation of CO and Other Heterogeneous Catalytic Studies by Employing a Layered Cu-Porphyrin Prepared Through Single-Crystal to Single-Crystal Exchange of a Zn Analogue.

A solvothermal reaction of Zn(NO ) ⋅6 H O, tetra-(4-pyridyl)porphyrin (H TPyP), and 4,4'-oxybis(benzoic acid) (H OBA) resulted in a new two-dimensional Zn- porphyrin metal-organic framework compound, Zn (C H N ) (C H O )(DMA)(H O) (1; DMA=N,N-dimethylacetamide). The Zn ions present in 1 could be exchanged by using a solution of Cu(NO ) ⋅3 H O in DMA at room temperature to give Cu (C H N ) (C H O )(DMA)(H O) (Cu∈1). The extra-framework solvent molecules have been shown to be reversibly removed or exchanged without collapse of the framework. Solvent-free Cu∈1 was explored as an active heterogeneous catalyst towards three different organic reactions: 1) the chemical fixation of CO into cyclic carbonate at room temperature and 1 atm; 2) the nitroaldol reaction under solvent-free conditions, and 3) the three-component coupling of aminopyridine, benzaldehyde, and aryl alkynes followed by 5-exo-dig cyclization to produce the important pharmacophore imidazopyridine.