Intramolecular Electron Transfer and Oxygen Transfer of Phosphomolybdate Molecular Wires

Phosphomolybdates with different P species exhibiting a 1D molecular structure are synthesized. The materials are constructed by a {[Mo^VI₆O₂₁]^6-} molecular tube as a shell with trapping a redox-active species P in the center. The building units ([(HP^IIIO₃)Mo^VI₆O₁₈]^2- or [(P^V₂O₇)Mo^VI₁₂O₃₆]^4-) form at room temperature, which further polymerize linearly along the c-axis. Interestingly, the material shows an unusual heat-triggered intramolecular redox property, which undergoes an electron-transfer-oxygen-transfer procedure from [{(HP^IIIO₃)Mo^VI₆O₁₈]^2-} to {[(P^V₂O₇)Mo^VI₁₂O₃₆]^4-}. The crystal structure of the material is stable during the oxidation reaction, while the central P is oxidized and the local structure changes.