Strong Attraction among the Fully Hydrophilic {Mo72Fe30} Macroanions

Abstract

We report the study on the unique driving forces of the self-assembly of fully hydrophilic, soluble {Mo₇₂Fe₃₀} macroanions into single-layer, vesicle-like “blackberry” structures in water and mixed solvents. The hydrophobic interaction that is responsible for the vesicle formation of amphiphilic surfactants does not contribute to the current blackberry formation because of the absence of hydrophobic moiety. The hydrogen bond, van der Waals force, and chemical interaction only play minor roles. Laser light scattering and conductance measurements on a series of {Mo₇₂Fe₃₀}/ethanol/H₂O solutions show that a certain amount of negative charges are necessary for the self-assembly, clearly indicating the existence of long-range attraction between macroanions, presumably due to the small counterions in between. The experimental results suggest that the charges on macroanions play a dual effect: short-range electrostatic repulsion and long-range “like-charge attraction”, which is the major source of attractive force between hydrophilic macroanions, while van der Waals force, hydrogen bonds, and temporary inter-{Mo₇₂Fe₃₀} Fe−O−Fe chemical linking may also have minor contributions.