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A series of molecular rotors was designed to study and measure the rate accelerating effects of an intramolecular hydrogen bond. The rotors form a weak neutral O–H⋯OC hydrogen bond in the planar transition state (TS) of the bond rotation process. The rotational barrier of the hydrogen bonding rotors was dramatically lower (9.9 kcal mol −1 ) than control rotors which could not form hydrogen bonds. The magnitude of the stabilization was significantly larger than predicted based on the independently measured strength of a similar O–H⋯OC hydrogen bond (1.5 kcal mol −1 ). The origins of the large transition state stabilization were studied via experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy, which has applications in catalyst design and in the study of enzyme mechanisms. 

Substituent–π interactions associated with aromatic stacking interactions were experimentally measured using a small N -phenylimide molecular balance model system. The direct interaction of the substituent (NH 2 , CH 3 , OH, F, Br, CF 3 and NO 2 ) with an aromatic ring was measured in the absence of the aromatic stacking interactions in solution. The measured substituent–π energies were found to correlate well with the Hammett σ m parameter similar to the substituent effects observed in aromatic stacking systems. The persistent electrostatic trends in substituent effects can arise from the direct electrostatic interactions between substituents and opposing π-systems. 

The influence of salts on the solvophobic interactions of two non-polar surfaces in organic solvent was examined using a series of molecular balances. Specific anion effects were observed that followed the Hofmeister series and enhanced the solvophobic effect up to two-fold. 

Herein, the control of a molecular rotor using hydrogen bonding guests is demonstrated. With a properly positioned phenol substituent, the N -arylimide rotors can form an intramolecular hydrogen bond that catalyses the rotational isomerization process. The addition of the guests disrupts the hydrogen bond and raises the rotational barrier, slowing the rotation by two orders of magnitude.