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

Abstract

The development of porous functional materials, using template copolymerization, that function in gas binding/release and catalysis is described. Using substitutionally inert metal complexes as templates, materials were prepared with immobilized sites that retained structural properties of the template; this allows for tunable functional properties. Chemical modification of the immobilized sites led to coordinatively unsaturated metal centers that reversibly bind either O2 or NO. Materials have also been prepared that exhibit varying degrees of catalytic activity in the hydrolytic kinetic resolution of epoxides as a function of the template concentration used to prepare the polymers.

Open Metal Sites within Isostructural Metal–Organic Frameworks for Differential Recognition of Acetylene and Extraordinarily High Acetylene Storage Capacity at Room Temperature

“…[1][2][3][4] Understanding the molecular recognition between the open metal sites and the substrate molecules at the molecular level will not only facilitate the discoveries of new catalysts, sensing, and storage materials, but will also provide a deep insight in the functions of the open metal sites in the biological systems and thus stimulate studies of modeling compounds to mimic biological functions. However, the highly reactive nature of such open metal sites has mainly limited our capacities to elucidate the metal-substrate recognition processes fundamentally and systematically within molecular assemblies.…”

Aspects of Immobilisation of Catalysts on Polymeric Supports

“…[138] Typical examples of imprinted transition metal complexes are the described in the following paragraphs. [138,139] Theoretically, molecular imprinting of metal complexes in bulk polymers should closely mimic the transition state of the rate-determining event. The imprinting often occurs via polymerisation of organic monomers such as ethylene glycol dimethacrylate, styrene and DVB to locate the complex in the bulk of the polymer matrix.…”

“…[139] A well-know example consists in the design of an aldolase MIP containing a cobalt complex coordinated with dibenzoylmethane. This complex is a reactive intermediate analogue in the aldol condensation of benzaldehyde and acetophenone.…”

Nitrogen Monoxide and Nitrous Oxide Binding and Reduction

“…The use of metal ion chemistry for such purposes is a very active area of research, i.e. to sense biological NO [23][24][25][26][27], deliver it as drug [28][29][30][31][32][33][34][35][36][37][38] or modulate NO concentrations (as in septic shock therapy [39,40]). Another form of cellular signaling is thought to also involve NO, but with biological thiols [41], consisting of nitrosylation-denitrosylation chemistry, i.e.…”