Phase stability of Keplerate-type polyoxomolybdates controlled by added cationic surfactant

Phase stability of two nanometer-scale Keplerate-type polyoxomolybdates, (NH4)42[MoVI72MoV60O372(CH3COO)30(H2O)72]⋅300H2O⋅10CH3COONH4 ({Mo132}) and MoVI72FeIII30O252L102⋅ca. 180H2O with L = H2O/CH3COO−/Mo2On−8/9 ({Mo72Fe30}), can be easily achieved by controlling the concentration of a cationic surfactant, tetradecyltrimethylammonium bromide (TTABr), in aqueous solution. Precipitates and floccules were observed when the stoichiometric ratios of rTTA+/{Mo132}rTTA+/{Mo132} and rTTA+/{Mo72Fe30}rTTA+/{Mo72Fe30} were 40:1 and 90:1, respectively, which were determined by zeta potential measurements. The surface charge properties and structure morphologies of {Mo132} and {Mo72Fe30} induced by controlling cationic TTABr in aqueous solution were determined by zeta potential measurements and transmission electron microscopy (TEM) observations. {Mo132} and {Mo72Fe30} can self-assemble into supramolecular “Blackberry” structures and exist at compositions less than the stoichiometric ratios of rTTA+/{Mo132}rTTA+/{Mo132} and rTTA+/{Mo72Fe30}rTTA+/{Mo72Fe30} in aqueous solution. Above the 1:1 stoichiometric ratio of TTABr/{Mo132} or TTABr/{Mo72Fe30}, the precipitates and floccules dissolve. Dynamic laser light scattering (DLS) measurements clearly demonstrated that the RhRh values have essentially no angular dependence at excess amounts of TTABr, suggesting the presence of spherically symmetric aggregates of {Mo132} and {Mo72Fe30}. Bilayer-like structures in aqueous solution were also demonstrated by TEM images. The interesting phase transition observed in our model systems of {Mo132} and {Mo72Fe30} macroanions with high chemical stability, similar shape, and masses could provide models for the understanding of more complex polyelectrolyte solutions and self-assembled soft magnetic materials and in bioapplications for highly selective adsorbents of proteins with different molecular sizes and charges.

Precipitation and dissolution of nanometer-scale macroanions by varying the concentration of a cationic surfactant to modify the surface charges can be readily achieved.Figure optionsDownload as PowerPoint slide