Synthesis Of Cui Immobilized On MOFs Material And The Application In Catalysis

Metal-Organic Frameworks (MOFs) represent a new class of hybrid organic-inorganicsurpramolecular materials with ordered networks formed from organic ligands and inorganicmetal cations. Owing to their high surface areas and tunable pore functionality, MOFs arecurrently under investigation for a variety of potential applications, including gas storage, gasseparations, and catalysis. These applications can be largely broadened by designingfunctional MOFs bearing an organic function on the organic linker or introducing the activesites to the MOFs, which can act as hosts for a variety of guest molecules.Of particular promise are frameworks with open metal centers, since these candramatically enhance gas uptakes or serve as a source of catalytic sites. The direct formationof frameworks bearing chelating ligand sites that are open to metal insertion is rare, sincetypically metal binding at these sites would occur during framework synthesis. Al(OH)(bpydc)(MOF-253) was synthesized by a hard oxophilic metal cation might preferentially coordinatethe carboxylate groups of a mixed donor ligand such as2,2’-bipyridine-5,5’-dicarboxylate(bpydc2-), leading to a framework with the softer donorgroups available to bind metals. Considering the2,2’-bipyridine (bpy) moieties are notcoordinated with any metal ions, MOF-253was selected as a host to support Cu active site.X-ray photoelectron spectroscopy (XPS) was used to identify the strong interaction betweenthe bpy and Cu atom in the MOF-253·0.5CuI.In this work, C-O bond forming cross-coupling reaction was selcected as a modelreaction to test the catalytic activity of the as-synthesized MOF-2530.5CuI. The novelMOF-253·0.5CuI-catalyzed coupling of a variety of benzene halides with phenols wasinvestigated under ligand-free conditions. In general, various aryl iodides reacted withelectron-rich phenols, electron-deficient phenols or phenols with strong steric hindrance togive the desired products in good to excellent yields(>80%) under very mild reactionconditions. Aryl bromides also afforded the desired products in good yields. Furthermore,various alcohols could be successfully coupled with iodobenzenes in good to excellent yields.It is well known that the O-arylation reaction of alcohols is much more difficult than phenols,especially in the presence of solvents. various aliphatic alcohols and alcohols with aromaticrings or aliphatic rings could be successfully coupled with iodobenzenes in good to excellentyields...