The molecular dynamics of three dipole functionalized hexa-peri-hexabenzocoronenes have been studied using site-specific NMR techniques and dielectric spectroscopy as a function of temperature and pressure. These probes (i) suggest that the thermodynamic state completely controls the dynamic response, (ii) clarify the origin of two dynamic processes associated with the presence of two glass temperatures, and (iii) provide the first phase diagram for substances of this kind.