Steric effects of substituted quinolines on lithium coordination geometry

• Published in: Polyhedron 2007-08, Vol.26 (14), p.3653-3660
• Main Authors: Rajeswaran, Manju, Begley, William J., Olson, Leif P., Huo, Shouquan
• Format: Article
• Language: English
• Subjects: Crystal structure; DFT calculations; Li coordination; Lithium complexes; OLED
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2007.03.054

Comparison of the solid-state structures of Li complexes, Liq, MeLiq, and PhLiq, illustrates steric effects on the coordination chemistry of lithium. Just by replacing the hydrogen in a quinoline ring with a methyl or phenyl changes the structure from a doubly stacked trimer to a paddle-wheel hexamer to a tetramer. The X-ray crystal structures of a series of lithium quinolates – lithium 8-hydroxyquinolinate (Liq), lithium 2-methyl-8-hydroxyquinolinate (MeLiq), and 2-phenyl-8-hydroxquinolinate (PhLiq), are compared. The substitution at the 2-position of the 8-hydroxyquinoline ligand has significant impact on the aggregation of the lithium complex in the crystalline state. Liq and MeLiq molecules crystallize as hexamers, whereas PhLiq crystallizes as a tetramer. The possible influence of crystal-packing forces on the preferred cluster structure was probed using density functional theory calculations on a systematically varied set of Liq, MeLiq, and PhLiq clusters. For Liq and MeLiq, the observed structures match the most stable computed structures. In the PhLiq case, the observed tetrameric structure is computed to be less stable (+1.2 kcal/mol/monomer) than the lowest energy structure, a hexamer. In this case, solid-state effects probably outweigh small differences in cluster stability.