The gas-phase lithium cation basicities (LCBs; Gibbs free energy of binding) of ethyl-, n-butyl-, and n-heptylbenzene have been measured by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The structures of the corresponding complexes and their relative stabilities were investigated through the use of B3LYP/6-311G(+)(3df,2p)//B3LYP/6-31G(d) density functional theory calculations. For n-butylbenzene and n-heptylbenzene, the most stable adducts correspond to pi complexes in which the alkyl chain coils toward the aromatic ring to favor its interaction with the metal cation. The extra stabilization provided by the flexible alkyl chain polarized by the charge on Li(+) is named the "scorpion effect". Conversely, these coiled conformations are among the least stable in the neutral system; they are not all stationary points on the potential-energy surface. The formation of complexes with a coiled alkyl chain leads to a significant enhancement of the Li(+) bonding energies (LBEs), which are approximately 20-30 kJ mol(-1) higher than those calculated for alkylbenzene pi complexes in which an uncoiled chain remains distant from the cation and thus minimizes the scorpion effect. This enhancement is less significant when LCBs are concerned, because the scorpion effect is entropically disfavored. There is very good agreement between the experimental Li(+) gas-phase basicities and the calculated values, provided that the statistical distribution of the conformers present in the gas phase is taken into account in this calculation.