Dynamic self-assembly of ions with variable size and charge in solution

Recently it was found that at ambient temperatures and in specific ternary solvents a cationic macrocyclic tetraimidazolium molecular box and small dianionic salts can self-assemble into highly defined, colloid-like ionic clusters, called ionoids. Here, we present evidence that the solution-based ionic self-assembly process leading to ionoids is a general phenomenon by characterizing new ionic building blocks which are capable of generating loosely bound globular and anisotropic structures similar to those in the established system. Using new cationic and anionic molecules, we show that variations in the size ratio between cationic and anionic component mainly affect size, shape and durability of the ionic clusters. Utilizing dynamic light scattering (DLS), continuously monitored phase-analysis light scattering (cmPALS) and continuous wave electron paramagnetic resonance (CW EPR) spectroscopy, we can thus define generalized ionic ratios, in which specific combinations of ionic compounds with certain size and charge densities are able to form these soft yet durable and long-lived ionic clusters. Furthermore, we characterize the temporal development of our dynamically self-assembled structures in solution from the level of the individual ionic building blocks to stable clusters with minimum lifetimes of months through previously established ionoid evolution diagrams (IEDs). The direct comparison of various cluster systems with respect to their shape, size and charges allows correlations of structural changes of the individual building blocks with the fate of self-assembled entities inside the crafted IEDs. This work generalizes the concept of ionoid formation to ions of specific sizes and charge densities, which may broaden the scope of this new type of highly dynamic and soft yet remarkably durable structures in the field of supramolecular chemistry.