Temperature dependence of the structure of a carbosilane dendrimer with terminal cyanobiphenyl groups: Molecular-dynamics simulation

Abstract

The molecular-dynamics simulation of the structure and molecular mobility of an individual macromolecule of a fourth-generation carbosilane dendrimer with terminal cyanobiphenyl groups in a highly diluted chloroform solution in the range 213–323 K is performed. Upon a change in temperature, the dendrimer undergoes structural rearrangement that depends on the ability of terminal segments to penetrate into the dendrimer. At temperatures close to the boiling point of the solvent, aliphatic spacers of terminal segments can penetrate deep into the dendrimer. As temperature decreases, the terminal segments are grouped only on the surface of the molecule; this leads to a 45% increase in the number of solvent molecules in the treelike part of the macromolecule. These results make it possible to give a new interpretation of temperature effects previously observed in NMR experiments for dilute solutions of these macromolecules.