A high-barrier molecular balance for studying face-to-face arene-arene interactions in the solid state and in...

An atropisomeric molecular balance was developed to study face-to-face arene-arene interactions. The balance has a large central 1,4,5,8-naphthalene diimide surface that forms intramolecular arene-arene interactions with two pendent arms. The balance adopts distinct syn and anti isomers with varying numbers of intramolecular interactions. Thus, the strength of the arene-arene interaction could be quantitatively measured by NMR spectroscopy from the anti/syn ratios. The size of the arene arms was easily varied, which allowed examination of the relationship between arene size and strength of the interaction. A nonlinear size dependence was observed in solution with larger arene arms having a disproportionately stronger arene-arene interaction. The intramolecular arene-arene interactions were also characterized in the solid state by X-ray crystallography. These studies were facilitated by the kinetic stability of the syn and anti isomers at room temperature due to the high isomerization barrier (DeltaG=27.0 kcal mol(-1)). Thus, the anti isomer could be selectively isolated and crystallized in its folded conformation. The X-ray structures confirmed that the anti isomers formed two strong intramolecular arene-arene interactions with face-to-face geometries. The solid-state structure analysis also reveals that the rigid framework may contribute to the observed nonlinear size trend. The acetate linker is slightly too long, which selectively destabilizes the balances with smaller arene arms. The larger arene arms are able to compensate for the longer linker and form effective intramolecular arene-arene interactions.