Solid Solid Phase Transitions and tert-Butyl and Methyl Group Rotation in an Organic Solid: X-ray Diffractometry, Differential Scanning Calorimetry, and Solid-State 1H Nuclear Spin Relaxation

Using solid-state H-1 nuclear magnetic resonance (NMR) spin lattice relaxation experiments, we have investigated the effects of several solid solid phase transitions on tert-butyl and methyl group rotation in solid 1,3,5-tri-tert-butylbenzene. The goal is to relate the dynamics of the tert-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 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 tert-butyl groups are disordered (that is, with a rotational 6-fold intermolecular potential dominating), to a triclinic phase (below 155 K), where the tert-butyl groups are ordered (that is, with a rotational 3-fold intermolecular potential dominating). This transition shows very different DSC scans when both a 4.7 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 tert-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 mo1(-1) range. In the low-temperature triclinic phase, the rotations of the tert-butyl groups and their methyl groups in the aromatic plane are quenched (on the NMR time scale). The two out-of-plane methyl groups in the tert-butyl groups are rotating with activation energies in the 5-11 kJ mol(-1) range.