NMR studies of solid nitrogen-containing dyestuffs
This thesis is concerned with the structural analysis of dyestuffs in their natural solid state by the application of solid-state nuclear magnetic resonance. These dysetuffs are all derived from the phenylazobenzene group, but tautomerism can produce structural changes, which have so far been uncharacterised in the solid-state for many of the dyestuffs currently under investigation. The information obtainable from (^13)C and (^15)N chemical shifts, both isotropic and anisotropic will be applied in this structure determination. Under magic-angle spinning the anisotropic nature of solid-state interactions is partially averaged or removed. The rotational resonance technique will be presented, which reintroduces the homonuclear dipolar interaction allowing dipolar coupling constants to be measured. Second-order effects arising from the (^14)N quadrupole interaction broaden spin-1/2 lines (RDC) in such a manner that bond lengths can be determined. This RDC analysis will be applied to a series of hydrazone structures to determine the (^15)N-(^14)N bond length within the hydrazone linkage. Finally, the two-dimensional magic-angle turning experiment will be discussed and applied to both the (13)C and (^15)N nuclei for a range of dyestuffs to show that accurate shielding tensor information can be obtained from large molecules.