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Dynamics of Dimethylbutanols in Plastic Crystalline Phases by Field Cycling ¹H NMR Relaxometry B

Carignani, Elisa, Forte, Claudia, Juszyńska-Gałązka, Ewa, Gałązka, Mirosław, Massalska-Arodź, Maria, Mandoli, Alessandro, Geppi, Marco, Calucci, Lucia
The Journal of physical chemistry 2018 v.122 no.42 pp. 9792-9802
alcohols, glass, liquids, magnetism, nuclear magnetic resonance spectroscopy, physical chemistry, temperature
2,2-Dimethylbutan-1-ol (2,2-DM-1-B), 3,3-dimethylbutan-1-ol (3,3-DM-1-B), and 3,3-dimethylbutan-2-ol (3,3-DM-2-B) show a rich solid-state polymorphism, which includes one or more plastic crystalline phases (also referred to as orientationally disordered crystalline (ODIC) phases) and glass of the liquid or ODIC phases. In this work, the dynamics of the three isomeric alcohols was investigated in the liquid and plastic crystalline phases by fast field cycling ¹H NMR relaxometry in the temperature range between 213 and 303 K. The analysis of the nuclear magnetic relaxation dispersion curves (i.e., longitudinal relaxation rate R₁ vs ¹H Larmor frequency) acquired for the different alcohols at different temperatures gave quantitative information on internal motions, overall molecular reorientations, and molecular self-diffusion. Self-diffusion coefficients were also determined in the liquid phase and in some ODIC phases of the samples from the trends of ¹H R₁ as a function of the frequency square root at low frequencies. Remarkable changes in the temperature trends of correlation times and self-diffusion coefficients were found at the transition between the liquid and the ODIC phase for 2,2-DM-1-B and 3,3-DM-1-B, and between ODIC phases for 3,3-DM-2-B, the latter sample showing a markedly different dynamic and phase behavior.