A Two-Step Intermolecular Interaction Of Molecular Macroions With Multivalent Counterions

Macroion-counterion interaction is essential for regulating the solution behaviors of hydrophilic macroions, as simple models for polyelectrolytes. Here, we explore the interaction between uranyl peroxide molecular cluster Li68K12(OH)20[UO2(O2)OH]60 (U60) and multivalent counterions. Different from interaction with monovalent counterions that shows a simple one-step process, isothermal titration calorimetry, combined with light/X-ray scattering measurements and electron microscopy, confirm a two-step process for their interaction with multivalent counterions: an ion-pairing between U60 and the counterion with partial breakage of hydration shells followed by strong U60-U60 attraction, leading to the formation of large nanosheets with severe breakage and reconstruction of hydration shells. The detailed studies on macroion-counterion interaction can be nicely correlated to the microscopic (self-assembly) and macroscopic (gelation or phase separation) phase transitions in the dilute U60 aqueous solutions induced by multivalent counterions. The molecular cluster U60 macroion exhibits a very different solution behavior depending on the valences of added counterions. When multivalent counterions are introduced, unlike monovalent counterions, there is an additional step for the macroion-counterion interaction. The two-step mechanism can be nicely correlated to the microscopic (self-assembly) and macroscopic (gelation) phase transitions observed in the macroionic aqueous systems. image