Solvation effects on self-association and segregation processes in tert-butanol-aprotic solvent binary mixtures

The present study reveals that the fully miscible binary mixtures consisting of tert-butanol with aprotic solvents form well-defined ordered supermolecular structures, which have been characterized on different length scales. Three different types of microstructures have been determined. They are separated by distinct crossovers that appear as a function of the dilution rate, going from "correlated clusters" to "diluted clusters" and "diluted monomer" microstructures. These observations have been made possible by the combination of Raman vibration spectroscopy, (1)H NMR, and neutron diffraction that probe, respectively, the cluster formation (self-association) and the intercluster correlations (cluster segregation). The solvation effects on both the cluster formation and the intercluster correlations have been assessed by tuning the alcohol-solvent interaction, i.e., changing the chemical nature of the diluting solvent from a purely inert alkane to a weakly interacting aromatic system.