Wheel-shaped polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- macroanions form supramolecular blackberry structure in aqueous solution

The hydrophilic polyoxotungstate [Cu20Cl(OH)(24)(H2O)(12)(P8W48O184)](25-) ({Cu20P8W48}) self-assembles into single-layer, hollow, spherical blackberry-type structures in aqueous solutions, as studied by dynamic light scattering (DLS), static light scattering (SLS), zeta potential analysis, and scanning electron microscopy (SEM) techniques. This represents the first report of blackberry formation for a non-Mo-containing polyoxometalate. There is no obvious change in the shape and size of the blackberries during the slow blackberry formation process, neither with macroionic concentration nor with temperature. Our results suggest that the blackberry-type structure formation is most likely a general phenomenon for hydrophilic macroions with suitable size and charge in a polar solvent, and not a specific property of polyoxomolybdates and their derivatives. The {Cu20P8W48} macroions are thus far the smallest type of macroions to date (equivalent radius < 2 nm) showing the unique self-assembly behavior, helping us to move one step closer toward identifying the transition point from simple ions (can be described by the Debye-Huckel theory) to macroions in very dilute solutions. Moreover, by using {Cu20P8W48} blackberry-type structures as the model system, the electrophoretic properties of macroionic supramolecular structures are studied for the first time via zeta-potential analysis. The mobility of blackberry- type structures is determined and used for understanding the state of small cations in solution. We notice that the average charge density on each {Cu20P8W48} macroanion in a blackberry is much lower than that of discrete free {Cu20P8W48} macroions. This result suggests that some small alkali counterions are closely associated with, or even incorporated into, the blackberry- type structures and thus do not contribute to solution conductivity. This model is fully consistent with our speculation that monovalent counterions play an important role in the self-assembly of macroions, possibly providing an attractive force contributing to blackberry formation.