Vanadium-Enhanced Intramolecular Redox Property of a Transition-Metal Oxide Molecular Wire.

Transition-metal oxide molecular wires are inorganic 1D polymers with elemental diversity. The properties of the materials are tuned by tuning the chemical compositions. The phosphovanadomolybdate molecular wire is synthesized, which is an isostructural material of the phosphomolybdate molecular wire. V is randomly located in the crystal to form {[(HPIIIO3)(MoVI5O15)(VVO3)]3-}n, which is incorporated into the material after the formation of the phosphomolybdate molecular wire. The heat-triggered redox reaction via the intramolecular electron-transfer and oxygen-transfer procedure is promoted after V substitution. Oxygen transfers from {VVO6} to {HPIIIO3}, and an electron transfers from {HPIIIO3} to {VVO6} with oxidation of the triangle {HPIIIO3} to the corner-sharing tetrahedral {PV2O7} and reduction of the octahedral {VVO6} to the pyramidal {VIVO5}. The material shows catalytic activity for the aerobic oxidation of alcohol to aldehyde, and good activity with high selectivity is obtained.