Institute of Physics of Rennes, CNRS-University of Rennes 1, UMR 6251, F-35042 Rennes, France.
J Phys Chem B. 2013 Sep 5;117(35):10221-30. doi: 10.1021/jp402380f. Epub 2013 Aug 26.
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.
本研究表明，由叔丁醇与质子惰性溶剂组成的完全互溶的二元混合物形成了具有明确有序的超分子结构，这些结构已在不同的尺度上进行了表征。确定了三种不同类型的微观结构。它们通过明显的交叉点隔开，这些交叉点作为稀释速率的函数出现，从“相关簇”到“稀释簇”和“稀释单体”微观结构。这些观察结果是通过拉曼振动光谱、(1)H NMR 和中子衍射的结合实现的，它们分别探测簇形成（自组装）和簇间相关性（簇分离）。通过调节醇-溶剂相互作用，即改变稀释溶剂的化学性质，从纯惰性烷烃到弱相互作用的芳烃体系，评估了溶剂化对簇形成和簇间相关性的影响。
