Strong toluenesulfonic and triflic acids were incorporated into a MIL-101 chromium(III) terephthalate coordination framework, producing hybrid proton-conducting solid electrolytes. These acid@MIL hybrid materials possess stable crystalline structures that do not deteriorate during multiple measurements or prolonged heating. Particularly, the triflic-containing compound demonstrates the highest 0.08 S cm(-1) proton conductivity at 15% relative humidity and a temperature of 60 °C, exceeding any of today's commercial materials for proton-exchange membranes. The structure of the proton-conducting media, as well as the long-range proton-transfer mechanics, was unveiled, in a certain respect, by Fourier transform infrared and (1)H NMR spectroscopy investigations. The acidic media presumably constitutes large separated droplets, coexisting in the MIL nanocages. One component of proton transfer appears to be related to the facile relay (Grotthuss) mechanism through extensive hydrogen-bonding interactions within such droplets. The second component occurs during continuous reorganization of the droplets, thus ensuring long-range proton transfer along the porous structure of the material.

The reaction of Na2WO4 and SeO2 under moderately acidic conditions yielded a novel 39-tungsto-6-selenite, [(Se2W12O46(WO(H2O))3](24-) (1), isolated as Na24[H6Se6W39O144]·74H2O. The macrocyclic polyanion consists of three {Se2W12} fragments connected via three trans-{WO(H2O)}(4+) groups. The same {Se2W12} building block is present in the structure of [(Se2W12O46)2{Mn2Cl(H2O)2}{Mn(H2O)2}2(SeO)2](13-) (2), which was obtained from the same reagents in the presence of MnCl2. The compounds were characterized by single-crystal X-ray diffraction, (77)Se NMR, Fourier transform infrared, and Raman spectroscopy.

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The compound Cs11(H3O)[Re6Se4(O)4Cl6]3.4H2O containing a novel cluster core {Re6Se4(O)4} with ordered ligands, where the 4 positions of one face of a Se4(O)4 cube are occupied exclusively by Se atoms and 4 O atoms lie in the opposite face was synthesized via the interaction of solid Re6Se8Br2 with molten KOH.