We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1 H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations.

We present and model the NMR frequency (8.50, 22.5, and 53.0 MHz) and temperature (97-300 K) dependence of the solid state 1H spin-lattice relaxation process in polycrystalline 1,4-dimethylphenanthrene. The solid state gives rise to a situation where methyl group rotation is the only motion on the NMR time scale and the relaxation rates due to the rotations of the 1- and 4-methyl groups are conveniently well-separated in temperature. At these low NMR frequencies, both the slow- and fast-motion limits are observed for the rotation of both methyl groups which allows for a more stringent test of the models. The relaxation is nonexponential as expected when it is caused by methyl group rotation in which case the initial relaxation rate is modeled. Parameters characterizing stretched-exponential fits of the relaxation process are also used both to quantify the degree of nonexponential relaxation and indicate that the observed relaxation is indeed due to the rotation of the two methyl groups. The results are compared with several other polycrystalline methylphenanthrenes and dimethylphenanthrenes. These systems allow for an investigation into how intramolecular and intermolecular interactions between methyl groups and neighboring atoms on the same and neighboring molecules determine the barriers to methyl group rotation.

We report solid-state nuclear magnetic resonance 1 H spin-lattice relaxation, single-crystal X-ray diffraction, powder X-ray diffraction, field emission scanning electron microscopy, and differential scanning calorimetry in solid samples of 2-ethylanthracene (EA) and 2-ethylanthraquinone (EAQ) that have been physically purified in different ways from the same commercial starting compounds. The solid-state 1 H spin-lattice relaxation is always non-exponential at high temperatures as expected when CH3 rotation is responsible for the relaxation. The 1 H spin-lattice relaxation experiments are very sensitive to the "several-molecule" (clusters) structure of these van der Waals molecular solids. In the three differently prepared samples of EAQ, the relaxation also becomes very non-exponential at low temperatures. This is very unusual and the decay of the nuclear magnetization can be fitted with both a stretched exponential and a double exponential. This unusual result correlates with the powder X-ray diffractometry results and suggests that the anomalous relaxation is due to crystallites of two (or more) different polymorphs (concomitant polymorphism).

Using solid-state 1H 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 mol-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.

We report a variety of experiments and calculations and their interpretations regarding methyl group (CH3) rotation in samples of pure 3-methylglutaric anhydride (1), pure 3-methylglutaric acid (2), and samples where the anhydride is slowly absorbing water from the air and converting to the acid [C6H8O3(1) + H2O → C6H10O4(2)]. The techniques are solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation, single-crystal X-ray diffraction, electronic structure calculations in both isolated molecules and in clusters of molecules that mimic the crystal structure, field emission scanning electron microscopy, differential scanning calorimetry, and high resolution 1H NMR spectroscopy. The solid state 1H spin-lattice relaxation experiments allow us to observe the temperature dependence of the parameters that characterize methyl group rotation in both compounds and in mixtures of the two compounds. In the mixtures, both types of methyl groups (that is, molecules of 1 and 2) can be observed independently and simultaneously at low temperatures because the solid state 1H spin-lattice relaxation is appropriately described by a double exponential. We have followed the conversion 1 → 2 over periods of two years. The solid state 1H spin-lattice relaxation experiments in pure samples of 1 and 2 indicate that there is a distribution of NMR activation energies for methyl group rotation in 1 but not in 2 and we are able to explain this in terms of the particle sizes seen in the field emission scanning electron microscopy images.

Lead iodide is a layered structure that experiences polytypism. The 2H polytype contains high rates of iodine vacancies but retains its stoichiometry. This characteristic feature makes it potentially useful for many practical applications. The hopping of iodine ions among vacancies is the dominant motion in the 2H polytype. We present a preliminary I and Pb solid-state nuclear magnetic resonance (NMR) spectroscopy and spin-lattice relaxation study of the 2H polytype below 400 K. We present reasonable models for the solid-state NMR results in terms of the effects of iodine hopping and lattice vibrations.

The dynamics of methyl (CH3) and fluoromethyl (CF3) groups in organic molecular (van der Waals) solids can be exploited to survey their local environments. We report solid state (1)H and (19)F spin-lattice relaxationexperiments in polycrystalline 3-trifluoromethoxycinnamic acid, along with an X-ray diffraction determination of the molecular and crystal structure, to investigate the intramolecular and intermolecular interactions that determine the properties that characterize the CF3 reorientation. The molecule is of no particular interest; it simply provides a motionless backbone (on the nuclear magnetic resonance(NMR) time scale) to investigate CF3 reorientation occurring on the NMR time scale. The effects of (19)F-(19)F and (19)F-(1)H spin-spin dipolar interactions on the complicated nonexponential NMRrelaxation provide independent inputs into determining a model for CF3 reorientation. As such, these experiments provide much more information than when only one spin species (usually (1)H) is present. In Sec. IV, which can be read immediately after the Introduction without reading the rest of the paper, we compare the barrier to CH3 and CF3 reorientation in seven organic solids and separate this barrier into intramolecular and intermolecular components.

We report solid-state (1) H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments, X-ray diffractometry, field-emission scanning electron microscopy, and both single-molecule and cluster ab initio electronic structure calculations on 1-methoxyphenanthrene (1) and 3-methoxyphenanthrene (2) to investigate the rotation of the methoxy groups and their constituent methyl groups. The electronic structure calculations and the (1) H NMR relaxation measurements can be used together to determine barriers for the rotation of a methoxy group and its constituent methyl group and to develop models for the two coupled motions.

We report solid state (1)H nuclear magnetic resonance spin-lattice relaxation experiments and X-ray diffractometry in 2-t-butyldimethylsilyloxy-6-bromonaphthalene. This compound offers an opportunity to simultaneously investigate, and differentiate between, the rotations of a t-butyl group [C(CH3)3] and its three constituent methyl groups (CH3) and, simultaneously, a pair of 'lone' methyl groups (attached to the Si atom). The solid state (1)H relaxation experiments determine activation energies for these rotations. We review the models for the dynamics of both 'lone' methyl groups (ones whose rotation axes do not move on the NMR time scale) and models for the dynamics of the t-butyl group and its constituent methyl groups (whose rotation axes reorient on the NMR time scale as the t-butyl group rotates).

We report a quantitative measure of the nonexponential (1)H spin-lattice relaxation resulting from methyl group (CH3) rotation in six polycrystalline van der Waals solids. We briefly review the subject in general to put the report in context. We then summarize several significant issues to consider when reporting (1)H or (19)F spin-lattice relaxation measurements when the relaxation is resulting from the rotation of a CH3 or CF3 group in a molecular solid.

Lead iodide is a layered structure that experiences polytypism. The 2H polytype contains high rates of iodine vacancies but retains its stoichiometry. This characteristic feature makes it potentially useful for many practical applications. The hopping of iodine ions among vacancies is the dominant motion in the 2H polytype. We present a preliminary I-127 and Pb-207 solid-state nuclear magnetic resonance (NMR) spectroscopy and spin-lattice relaxation study of the 2H polytype below 400 K. We present reasonable models for the solid-state NMR results in terms of the effects of iodine hopping and lattice vibrations.

We report ab initio density functional theory electronic structure calculations of rotational barriers for t-butyl groups and their constituent methyl groups both in the isolated molecules and in central molecules in clusters built from the X-ray structure in four t-butyl aromatic compounds. The X-ray structures have been reported previously. We also report and interpret the temperature dependence of the solid state 1H nuclear magnetic resonance spin-lattice relaxation rate at 8.50, 22.5, and 53.0 MHz in one of the four compounds. Such experiments for the other three have been reported previously. We compare the computed barriers for methyl group and t-butyl group rotation in a central target molecule in the cluster with the activation energies determined from fitting the 1H NMR spin-lattice relaxation data. We formulate a dynamical model for the superposition of t-butyl group rotation and the rotation of the t-butyl group's constituent methyl groups. The four compounds are 2,7-di-t-butylpyrene, 1,4-di-t-butylbenzene, 2,6-di-t-butylnaphthalene, and 3-t-butylchrysene. We comment on the unusual ground state orientation of the t-butyl groups in the crystal of the pyrene and we comment on the unusually high rotational barrier of these t-butyl groups.

We bring together solid state (1)H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH3) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The (1)H relaxation measurements, on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The (1)H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 2-12 kJ mol(-1) range.

This paper brings together field emission scanning electron microscopy, single-crystal X-ray diffraction, and density functional electronic structure calculations in both an isolated molecule and a cluster of seven whole and fourteen half molecules of 4,4'-dimethoxybiphenyl to investigate coupled methyl-group rotation (over a barrier) and methoxy-group libration (meaning a rotation from the ground state not all the way to the transition state and back again). The structure of the isolated molecule, determined by the electronic structure calculations, is compared with the structure of the molecule found in the crystal. As the methyl group rotates from its ground state to its transition state, the methoxy group rotates 30° in the isolated molecule and 16° in the cluster. The calculated barriers for this coupled methyl-group rotation and methoxy group libration in the isolated molecule and in the crystal are 12.8 kJ mol(-1) and 10.3 kJ mol(-1) respectively, suggesting that intermolecular interactions in the crystal lower the barrier. These barriers are compared with the value of 11.5±0.5 kJ mol(-1) obtained from solid-state (1)H spin-lattice relaxation measurements [P. A. Beckmann and E. Schneider, J. Chem. Phys. 2012, 136, 054508.].

We report (1)H spin-lattice relaxation measurements in polycrystalline 4,4'-dimethoxybiphenyl at temperatures between 80 and 300 K at NMR frequencies of ω(0)/2π = 8.50, 22.5, and 53.0 MHz. The data are interpreted in terms of the simplest possible Bloch-Wangsness-Redfield methyl group hopping model. Different solid states are observed at low temperatures. The (1)H spin-lattice relaxation is nonexponential at higher temperatures where a stretched-exponential function fits the data very well, but this approach is phenomenological and not amenable to theoretical interpretation. (We provide a brief literature review of the stretched-exponential function.) The Bloch-Wangsness-Redfield model applies only to the relaxation rate that characterizes the initial (1)H magnetization decay in a high-temperature nonexponential (1)H spin-lattice relaxation measurement. A detailed procedure for determining this initial relaxation rate is described since large systematic errors can result if this is not done carefully.

We investigate the relationship between intramolecular rotational dynamics and molecular and crystal structure in 4,4'-dimethoxyoctafluorobiphenyl. The techniques are electronic structure calculations, X-ray diffractometry, and (1)H and (19)F solid state nuclear magnetic resonance relaxation. We compute and measure barriers for coupled methyl group rotation and methoxy group libration. We compare the structure and the structure-motion relationship in 4,4'-dimethoxyoctafluorobiphenyl with the structure and the structure-motion relationship in related compounds in order to observe trends concerning the competition between intramolecular and intermolecular interactions. The (1)H spin-lattice relaxation is nonexponential in both the high-temperature short-correlation time limit and in the low-temperature long-correlation time limit, albeit for different reasons. The (19)F spin-lattice relaxation is nonexponential at low temperatures and it is exponential at high temperatures.