Intramolecular Electron Transfer and Oxygen Transfer of Phosphomolybdate Molecular Wires

Zhenxin Zhang; Masahiro Sadakane; Michikazu Hara; Yanshuo Li; Wataru Ueda

doi:10.1021/acs.inorgchem.9b01744

Intramolecular Electron Transfer and Oxygen Transfer of Phosphomolybdate Molecular Wires

Inorg Chem. 2019 Sep 16;58(18):12272-12279. doi: 10.1021/acs.inorgchem.9b01744. Epub 2019 Aug 29.

Authors

Zhenxin Zhang¹, Masahiro Sadakane², Michikazu Hara³, Yanshuo Li¹, Wataru Ueda⁴

Affiliations

¹ School of Material Science and Chemical Engineering , Ningbo University , Fenghua Road 818 , Ningbo , Zhejiang , 315211 , P. R. China.
² Department of Applied Chemistry , Hiroshima University , 1-4-1 Kagamiyama , Higashi Hiroshima 739-8527 , Japan.
³ Materials and Structures Laboratory , Tokyo Institute of Technology , Nagatsuta-cho 4259 , Midori-ku, Yokohama , 226-8503 , Japan.
⁴ Faculty of Engineering , Kanagawa University , Rokkakubashi , Kanagawa-ku, Yokohama , 221-8686 , Japan.

PMID: 31465205
DOI: 10.1021/acs.inorgchem.9b01744

Abstract

Phosphomolybdates with different P species exhibiting a 1D molecular structure are synthesized. The materials are constructed by a {[Mo^VI₆O₂₁]^6-}_n 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-}_n to {[(P^V₂O₇)Mo^VI₁₂O₃₆]^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.