Two model compounds, lithium imidazoliurn (LiIm) and lithium 2-undecylimidazolium (und-LiIm), were synthesized. These materials are chosen as models of potential lithium ion conductors for use as electrolytes in lithium batteries. Solid-state NMR was used to provide information on the microscopic interactions including ionic mobility and ring reorientations which govern the efficiency of conductivity. Lithium imidazolium was mixed with lithium methylsulfonate, generating a doped complex in which a doubly lithiated imidazole ring was inferred based on the Li-7 NMR chemical shifts. Our research includes Li-6,Li-7 variable temperature MAS NMR experiments at intermediate spinning speeds, relaxation studies to determine spin-lattice relaxation times (T-1) of lithium ion hopping, and 2D exchange spectroscopy to determine possible chemical exchange processes. The possibility of 2-site ring reorientation for the doubly lithiated imidazole ring was supported by exchange spectroscopy. Comparisons of spin-lattice relaxation times and corresponding activation energies of the lithium imidazolium and the doped complex point to a higher degree of mobility in the latter. Lithium 2-undecylimidazolium was prepared and exhibited a lower melting point than the parent lithium imidazolium, as expected. This small 7 molecule was chosen as representative of a side-chain functionalized polyethylene-based material. Li-7 MAS spectra show mainly the presence of the doubly lithiated imidazole ring in pure und-LiIm, and in the LiCH3SO3-und-LiIm mixture. The data clearly indicate local mobility of the lithium ions in the materials. (c) 2006 Elsevier B.V. All rights reserved.