Comparative studies on the nature and kinetics of phase transitions in plastic crystals: Hydrogen-bonded adamantane derivatives

Abstract

In this paper, the results of thermal, structural, and spectroscopic studies on 3-amino-1-adamantanol (3-NH2-1-OH-ADM) were discussed with those recently published for 1-hydroxyl and 1-amine derivatives of adamantane (1-OH-ADM, 1-NH2-ADM). Calorimetric measurements showed that the examined compound, like 1-NH2-ADM, is characterized by multiple thermal events in the thermogram measured on heating and cooling. Further X-ray diffraction, Fourier-transform infrared, and Raman spectroscopy investigations suggested that two of them correspond to the transition from the ordinary crystal (OC) to the plastic crystal (PC) phase I and the transition between two PC phases (PC(I) and PC(II)), while the third subtle one is rather not related to a phase transition. Interestingly, ambient pressure dielectric studies performed during heating and cooling cycles revealed changes in the imaginary and real parts of the complex dielectric permittivity at temperatures close to the temperatures of phase transitions detected by the calorimetry. Such behavior resembled that reported for 1-NH2-ADM. Finally, isothermal time-dependent dielectric and infrared studies, supported by the analysis of asynchronous 2D-IR correlation spectra, indicated that the first endothermic peak, visible in the thermogram of 3-NH2-1-OH-ADM over an enormously large temperature interval and related to the OC-PC(I) phase transition, similarly to the one, assigned to the PC(I)-PC(II) transition in 1-NH2-ADM, has a character of the kinetic process. Importantly, during the annealing of 3-NH2-1-OH-ADM at T = 328–343 K, we observed a clear change in the dc-conductivity as well as intramolecular dynamics related to the vibrations of CH, NH2, and OH moieties that occur at different rates.