Coordination of Terpyridine to Li+ in Two Different Ionic Liquids

On the basis of 7Li NMR experiments, the complex-formation reaction between Li+ and the tridentate N-donor ligand terpyridine was studied in the ionic liquids [emim]­[NTf2] and [emim]­[ClO4] as solvents. For both ionic liquids, the NMR data implicate the formation of [Li(terpy)2]+. Density functional theory calculations show that partial coordination of terpyridine involving the coordination of a solvent anion can be excluded. In contrast to the studies in solution, X-ray diffraction measurements led to completely different results. In the case of [emim]­[NTf2], the polymeric lithium species [Li­(terpy)­(NTf2)]n was found to control the stacking of this complex, whereas crystals grown from [emim]­[ClO4] exhibit the discrete dimeric species [Li­(terpy)­(ClO4)]2. However, both structures indicate that each lithium ion is formally coordinated by one terpy molecule and one solvent anion in the solid state, suggesting that charge neutralization and π stacking mainly control the crystallization process.