A wheel-shaped Zr-substituted phosphotungstate [{Zr(C2O4)2}3 (PO4)(P6W39O150)]39- with tunable proton conduction properties.

A wheel-shaped Zr-substituted phosphotungstate, [N(CH3)4]2K16Na10.5H10.5[{Zr(C2O4)2}3(PO4)(P6W39O150)]·45H2O (1), was synthesised from a hexavacant Dawson-type precursor [H2P2W12O48]12-via a conventional solution method. Compound 1 features a wheel-shaped polyanion comprising an annular [P6W39O150]36- cluster supported by a turbine-shaped [{Zr(C2O4)2}3(PO4)]3- fragment, with three oxalate groups covalently anchored to W atoms. Compound 1 was systematically characterized by IR, UV, PXRD, TGA and 31P NMR spectra. The 31P NMR spectra over time were monitored to verify the stability of 1 in aqueous solution. This compound possesses remarkable proton conductive behavior with a high conductivity of 1.18 × 10-2 S cm-1 at 368 K.