We
characterize the influence of preferential solvation on the
dynamic self-assembly process between small dianionic salts and a
macrocyclic tetraimidazolium molecular box into highly defined, colloidlike
ionic clusters in solution, called ionoids. Here, we substitute individual
solvents in the established optimal ternary solvent mixture dimethyl
sulfoxide (DMSO)/glycerol/water 50:43:7 (v/v/v), namely, DMSO through
dimethyl formamide, glycerol through ethylene glycol and water through N-methylpropionamide, and such can characterize the changes
in shape and size of the structures of loosely bound ionic clusters
induced by the substitution of a specific solvent component. Using
dynamic light scattering we associate size, shape, and initial durability
of ionic clusters with solvent parameters like dynamic viscosity and
relative permittivity to highlight the importance of solvent composition
for the build-up of globular ionoids as well as anisotropic ionic
clusters. To further analyze the solvation state of our dianionic building unit inside
the initial ion cloud state, which later affects the self-assembly
process of ionic clusters, we perform continuous wave (CW) electron
paramagnetic resonance spectroscopy measurements at X-band (∼9.4
GHz) and Q-band (∼34 GHz) frequencies.