Structural and reactivity insights into covalently linked Cu(i) complex-Anderson polyoxometalates.

The synthesis, crystallographic analysis and full characterization of the Cu(i) complex-functionalized Anderson polyoxomolybdate anions (nBu4N)[MMo6O18((OCH2)3CNCH(C47H37N2P2OCu)2)] (M = Mn3+, Fe3+, Co3+) is reported. For the first time, direct crystallographic evidence for the covalent attachment of a photoactive metal complex to an organo-functionalized polyoxometalate is obtained. Initial electrochemical and photochemical studies report fundamental properties and solution stability of the compounds.

"CLICKable" azide-functionalized phosphonates for the surface-modification of molecular and solid-state metal oxides.

The covalent functionalization of metal oxide surfaces with organic ligands gives unique organic-inorganic hybrids. Here we report a bifunctional organic tether combining a phosphonate for metal oxide anchoring with an organic azide for attachment of organic groups. Stable binding of the tether to molecular and solid-state metal oxides is demonstrated and the subsequent "CLICKability" of the TiO2-anchored tether is shown. The phosphonate-azide reported could in future allow the general linkage of functional organic groups to metal oxides.