Bulk Inclusions of Double Pyridazine Molecular Rotors in Hexagonal Tris( o-phenylene)cyclotriphosphazene.

Abstract

A new generation of double pyridazine molecular rotors differing in intramolecular dipole-dipole spacing was synthesized. All rotor molecules formed bulk inclusions in a tris( o-phenylenedioxy)cyclotriphosphazene (TPP) host. Results of dielectric spectroscopy were fitted to a pair of nine-state models that accounted for interactions of neighboring dipoles at either an aligned or opposed possible orientation of the local threefold dipole rotation potentials within a channel of the TPP host. The results indicate dipole-dipole interaction strengths at the 100 to 200 K scale that lead dipoles to preferentially populate a subset of low-energy configurations. They also reveal that pyridazines with ethynyl substituents in 3- and 6-positions have slightly higher rotational barriers (3.2-3.5 kcal/mol) than those carrying one ethynyl and one tert-butyl group (1.9-3.0 kcal/mol). Upon cooling, these barriers reduce the rate of thermal transitions between the potential wells so much that the inclusions cannot achieve ordered dipolar ground states.