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Three new group IIIA metal phosphate–oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]·H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (σ) of 9.09 × 10−3 S cm−1 at 85 °C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs. [ABSTRACT FROM AUTHOR]

The first transition-metal-bridged polyniobotungstate-based 3D framework has been hydrothermally synthesized, which is constructed from bi-[CuII(en)2(H2O)]-decorating [Nb3W3O19]5− polyoxoanions linked together by CuI ions. Interestingly, the 3D polyniobotungstate framework can undergo a solid–liquid reaction with KI solution to generate a 1D copper halide of [Cu(en)2][CuI2]2 in a single-crystal-to-single-crystal process. [ABSTRACT FROM AUTHOR]