Metal-Organic Framework Based on Heptanuclear Cu-O Clusters and Its Application as a Recyclable Photocatalyst for Stepwise Selective Catalysis

Visible-light driven photoreactions using metal-organic frameworks (MOFs) as catalysts are promising with regard to their environmental friendly features such as the use of renewable and sustainable energy of visible light and potential catalyst recyclability. To develop potential heterogeneous photocatalysts, a family of three copper(II) coordination polymers bearing different Cu-O assemblies have been synthesized with the ligand 4,4'-disulfo-[1,1'-biphenyl]-2,2'-dicarboxylate acid (H4DSDC), namely, {[Cu-7(DSDC)(2)(OH)(6)(H2O)(10)]center dot xH(2)O}(n) (1), {[Cu-4(DSDC)(4,4'-bpy)(2)(OH)(4)]center dot 2H(2)O}(n) (2), and (Cu-2(DSDC)(phen)(2)(H2O)(2)}(n) (3) (4,4'-bpy = 4,4'-bipyridine and phen = 1,10-phenanthroline). Complex 1 represents a metal-organic framework featuring a NbO type topology constructed from the infinite linkage of heptanuclear [Cu-7(mu(3)-OH)(6)(H2O)(10)](8+) clusters by deprotonated DSDC4- ligands, comprising one-dimensional hexagonal channels of a diameter around 11 angstrom that are filled with water molecules. The infinite waving {[Cu-2(OH)(2)](2+)}(n) ladderlike chains in complex 2 are bridged by DSDC4- and 4,4'-bpy ligands into a three-dimensional framework. A two-dimensional layered structure is formed in complex 3 due to the existence of terminal phenanthroline ligands. All of the coordination polymers 1-3 are able to catalyze the visible-light driven oxidation of alcohols at mild conditions using hydrogen peroxide as an oxidant, in which complex 1 demonstrates satisfactory efficiency. Significantly for this photoreaction catalyzed by 1, the extent of oxidation over aryl primary alcohols is fully controllable with time-resolved product selectivity, giving either corresponding aldehydes or carboxylate acids in good yields. It is also remarkable that the photocatalyst could be recovered almost quantitatively on completion of the catalytic cycle without any structure change, and could be recycled for catalytic use for at least five cycles with constant efficiency. This photocatalyst with time-resolved selectivity for different products may provide new insight into the design and development of novel catalytic systems.