Solid Solid Phase Transitions and tert-Butyl and Methyl Group Rotation in an Organic Solid: X-ray Diffractometry, Differential Scanning Calorimetry, and Solid-State H-1 Nuclear Spin Relaxation
Final Published Version
Journal of Physical Chemistry A
Using solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments, we have investigated the effects of several solid-solid phase transitions on t-butyl group and methyl group rotation in solid 1,3,5-tri-t-butylbenzene. The goal is to relate the dynamics of the t-butyl groups and their constituent methyl groups to properties of the solid determined using single-crystal X-ray diffraction and differential scanning calorimetry (DSC). On cooling, the DSC experiments see a first-order, solid-solid phase transition at either 268 K or 155 K (but not both) depending on thermal history. The 155 K transition (on cooling) is identified by single-crystal X-ray diffraction to be one from a monoclinic phase (above 155 K) where the t-butyl groups are disordered (that is, with a rotational six-fold intermolecular potential dominating) to a triclinic phase (below 155 K) where the t-butyl groups are ordered (that is, with a rotational threefold intermolecular potential dominating). This transition shows very different DSC scans when both a 5 mg polycrystalline sample and a 19 mg powder sample are used. The 1H spin-lattice relaxation experiments with a much larger 0.7 g sample are very complicated and, depending on thermal history, can show hysteresis effects over many hours and over very large temperature ranges. In the high-temperature monoclinic phase, the t-butyl groups rotate with NMR activation energies (closely related to rotational barriers) in the 17-23 kJ mol-1 range and the constituent methyl groups rotate with NMR activation energies in the 7-12 kJ mol-1 range. In the lowtemperature triclinic phase, the rotations of the t-butyl groups and their methyl group in the aromatic plane are quenched (on the NMR time scale). The two out-of-plane methyl groups in the t-butyl groups are rotating with activation energies in the 5-11 kJ mol-1 range.
Beckmann, P.A., McGhie, A.R., Rheingold, A.L., Sloan, G.J., Szewczyh, S.T. "Solid Solid Phase Transitions and tert-Butyl and Methyl Group Rotation in an Organic Solid: X-ray Diffractometry, Differential Scanning Calorimetry, and Solid-State H-1 Nuclear Spin Relaxation." Journal of Physical Chemistry A, 121.33 (2017): 6220-6230.