London Dispersion in Alkane Solvents.

The importance of London dispersion interactions in solution is an ongoing debate. Although the significance of dispersion for structure and stability is widely accepted, the degree of its attenuation in solution is still not properly understood. Quantitative evaluations are derived mostly from computations. Experimental data provide guidelines to include London dispersion in solution phase design. Herein, dispersive interactions were examined with an azobenzene probe. Alkyl substituents in meta positions of the azobenzene core were systematically varied and the effect on the half-lives for the thermally induced Z to E isomerization in several alkane solvents was determined. The results show that intramolecular dispersion is only marginally influenced. In solvents with low surface tension, reduced destabilizing solvent-solvent interactions increase the half-life up to 20 %. Specific individual interactions between alkyl chains on the azobenzene and those of the solvent lead to additional fluctuations of the half-lives. These presumably result from structural changes of the conformer ensemble.