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 {[MoVI6O21]6-}n molecular tube as a shell with trapping a redox-active species P in the center. The building units ([(HPIIIO3)MoVI6O18]2- or [(PV2O7)MoVI12O36]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 [{(HPIIIO3)MoVI6O18]2-}n to {[(PV2O7)MoVI12O36]4-}n/2. The crystal structure of the material is stable during the oxidation reaction, while the central P is oxidized and the local structure changes.