Development of Porous Materials for Heterogeneous Catalysis: Kinetic Resolution of Epoxides.

Abstract

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Confinement of Metal Complexes within Porous Hosts: Development of Functional Materials for Gas Binding and Catalysis

“…Scheme 1 outlines the general copolymerization process used to prepare our porous materials. 5,6 This methodology in principle allows for partial control of the size and shape of the immobilized sites within a network polymer. We reasoned that this method could be applied to the design and preparation of new multidentate ligands dispersed throughout a porous material.…”

“…14 We, too, use molecular precursors as building blocks for porous materials. 5,6 Copolymerization of the inert metal templates with excess cross-linker results in materials that are sufficiently rigid, allowing for retention of the immobilized site and pore structure generated during polymerization. The porosity of the host allows substrate and solvent access to the immobilized sites within the material.…”

“…16 Using inorganic templates, we take advantage of the inherent properties of metal complexes and can utilize spectroscopic methods that are selective for metal ions, such as X-ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopies. 5,6,17 Using this approach, we developed an endogenous ligand-binding assay involving unsaturated Co II complexes to analyze immobilized site structure. 5a,b This assay uses square planar [Co II salen] complexes (salen, bis[2-hydroxybenzaldehyde]ethylene-diiminate), which are known in solution to weakly bind a fifth ligand (e.g., O 2 or pyridine) with association constants of less than 100 M -1 .…”

“…We have utilized template copolymerization, a method used to prepare molecularly imprinted polymers, 2, 3,4 to prepare functional porous materials derived from metal-based molecular precursors. 5,6 This strategy is advantageous because it potentially allows for structural control over the coordination spheres of metal complexes after immobilization into a porous host. This Account describes our recent efforts in developing materials that exhibit function in the storage and release of dioxygen 5a,b and nitric oxide 5c,d and in catalysis.…”

“…This Account describes our recent efforts in developing materials that exhibit function in the storage and release of dioxygen 5a,b and nitric oxide 5c,d and in catalysis. 6…”