Abstract
We report on electrostatically complexed materials bearing advanced functions that are not possible for other assemblies. The fundamentals of electrostatic association between oppositely charged polyelectrolytes and colloidal particles are introduced together with the conditions needed for complexation, including those related to ionic strength, pH, and hydration. Related considerations allow us to control the properties of the formed complexes and to develop features such as self-healing and underwater adhesion. In contrast to assemblies produced by typical hydrophobic and chemical interactions, electrostatic complexation leads to reversible systems. A state-of-the-art account of the field of electrostatically complexed materials is provided, including those formed from biomolecules and for salt-controlled rheology, underwater adhesiveness, and interfacial spinning. Finally, we present an outlook of electrostatic complexation from the colloidal chemistry perspective.