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Solid-state NMR spectroscopy is used to investigate strong hydrogen bonds in a variety of solids. NMR measurements of the 2H nuclear quadrupole coupling (CQ) and nuclear magnetic shielding tensors are performed on samples of trimethylammonium chloride (TMAC), protonated 1,8-bis(dimethylamino)napthalene (DMANH+), and potassium and sodium bifluoride. 2H CPMAS is used to obtain high quality spectra while reducing experimental time. From spectral simulations, values of 127, 36, 59 and 58 kHz are determined for the 2H CQ of TMAC, DMANH+ CF3SO3-, NaHF2 and KHF2, respectively. The 2H CPMAS spectrum of TMAC shows a minor secondary component resulting from a solid phase in which the trimethylammonium cation is experiencing precessional motion. At high temperature the 2H CPMAS spectrum of DMANH+ shows unexpected spinning sideband lineshapes because of residual dipolar coupling to 14N. The experimental 2H CQ values are corroborated by ab-initio and DFT calculations; for DMAN and the bifluorides the 2H CQ values are averaged over the potential energy surface to improve the computational quality. Large values of the isotropic chemical shift (>10 ppm) are observed for all of the hydrogen-bonded deuterons. To complement the 2H NMR work, other nuclei in the compounds of interest are investigated, for TMAC these include: 35Cl, 37Cl, 1H, 14N, 15N. The 35Cl CQ shows a small, but observable deuterium/proton isotope effect. Quadrupolar and chemical shift parameters for assorted nuclei in TMAC are calculated at various N-H distances, demonstrating the strong dependence of the chlorine and hydrogen parameters on the proton position. For DMANH+ the 15N CPMAS spectrum of a static sample of DMANH+-d1 provides a value for the average dipolar 15N-D coupling constant of 870±30 Hz, corresponding to a distance of 1.29 A. Spectra of the counterions in the bifluoride salts are obtained, providing CQ values of 123 kHz and 1.141 MHz for 39K and 23Na, respectively.

Halogen bonding to phosphorus atoms remains uncommon, with relatively few examples reported in the literature. In part 1 of the thesis, the preparation and investigation of the cocrystal (dicyclohexylphenylphosphine)(1,6-diiodoperfluorohexane) by X-ray crystallography and solid-state multinuclear magnetic resonance spectroscopy is described. The crystal structure features two crystallographically unique C-I···P halogen bonds (dI···P = 3.090(5) Å, 3.264(5) Å) and crystallographic disorder of one of the 1,6-diiodoperfluorohexane molecules. The first of these is the shortest and most linear I···P halogen bond reported to date. 13C, 19F, and 31P magic-angle spinning solid-state NMR spectra are reported. A 31P chemical shift change of -7.0 ppm in the cocrystal relative to pure dicyclohexylphenylphosphine, consistent with halogen bond formation, is noted. This work establishes iodoperfluoroalkanes as viable halogen bond donors when paired with phosphorus acceptors, and also shows that dicyclohexylphenylphosphine can act as a practical halogen bond acceptor. In part 2 of the thesis, computational work was done on nuclides of atoms which engage in the strongest halogen bonds (iodine, bromine, chlorine) that are all quadrupolar (spin I > ½). Previous group work reported extensive experimental NMR and NQR data relating 35/37Cl, 79/81Br, and 127I quadrupolar coupling information to local molecular structure in halogen bonded systems. Here, we make use of a new parameter, the valence p-orbital population anisotropy (VPPA), reported by Rinald and Wu, to increase our understanding of the origins of the electric field gradients (EFG) in halogen-bonded systems. Computations on model and real halogen-bonded cocrystalline systems using standard hybrid DFT methods are used to generate p-orbital populations and to compute the VPPA. We discuss the utility of the VPPA, and hence the EFG, as a tool to assess the ability of particular donors to engage in halogen bonds.

Abstract The subjects of this thesis are the dynamics of liquid crystals in external electric and magnetic fields as well as the magnetic properties of small molecules, both studied by liquid crystal nuclear magnetic resonance (LC NMR) spectroscopy. Director dynamics of a liquid crystal 5CB in external magnetic and electric fields was studied by deuterium NMR and spectral simulations. A new theory was developed to explain the peculiar oscillations observed in the experimental spectra collected during fast director rotation. A spectral simulation program based on this new theory was developed and the outcome of the simulations was compared with the experimental results to verify the tenability of the theory. In the studies on the properties of small solute molecules, LC NMR was utilised to obtain information about anisotropic nuclear magnetic interaction tensors. The nuclear magnetic shielding tensor was studied in methyl halides, the spin-spin coupling tensor in methyl mercury halides and the quadrupolar coupling tensor in deuterated benzenes. The effects of small-amplitude molecular motions and solvent interactions on the obtained parameters were considered in each case. Finally, the experimental results were compared to the corresponding computational NMR parameters calculated in parallel with the experimental work.

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