Abstract
A coordination macrocycle composed of eight identical [PMo8O27]- ({PMo8}) clusters connected by both organic tetraphosphonates and inorganic phosphates, (C3N2H5)29(NH4)6H12[(PMo8O27)8(C10P4O12N2H20)4(PO4)4Cs(Mo4O10(H2O)4)] (C3N2H5+ = imidazolium), is presented here. The primary building block, {PMo8}, is a tetravacant Keggin-type phosphomolybdate that has never been observed before. The compound shows a high proton conductivity of 9.70 × 10-3 S cm-1 at 373 K and 98% relative humidity. Control experiments on an imidazolium-free sample demonstrate the critical role of the imidazolium counterions as mobile proton carriers. The contribution of imidazolium necessitates a high activation energy (Ea = 0.502 eV) for proton conduction via the vehicle mechanism.
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