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Intramolecular Electron Transfer and Oxygen Transfer of Phosphomolybdate Molecular Wires

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journal contribution
posted on 29.08.2019, 18:08 by Zhenxin Zhang, Masahiro Sadakane, Michikazu Hara, Yanshuo Li, Wataru Ueda
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.

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