Tris-o-phenylenedioxycyclotriphosphazene (TPP) inclusion compounds containing a dipolar molecular rotor

Article abstract of DOI:10.1021/cg4013608

A rod-shaped molecular rotor consisting of a p-terphenyl shaft attached to p-carborane whose antipodal position carries a dipolar 2,3-dichlorophenyl rotator forms an inclusion compound with hexagonal tris-o- phenylenedioxycyclotriphosphazene (TPP). Results of solid-state NMR spectroscopy, X-ray powder diffraction, dielectric loss spectroscopy, and density functional theory calculations lead us to propose that the whole molecule inserts into the TPP channels, with the rotator located in the outermost surface layer. Although the placement and alignment of the dipoles at the surface appear favorable, the sample does not exhibit collective behavior even at 7 K, presumably due to the relatively large barrier to rotation (～8.6 kcal/mol). In incompletely annealed samples of the inclusion compound, some of the rotators protrude outside the surface and have a rotational barrier of ～3.4 kcal/mol. In the inclusion compound of an analog in which the rotator is replaced with a methyl group, some of the methyl substituents are located inside the surface layer of TPP and others protrude above it.