Relationship between interaction geometry and cooperativity measured in H-bonded networks of hydroxyl groups

Abstract

Cooperativity between interactions in H-bonded networks can increase the strengths of H-bonds involving hydroxyl groups by up to 50%. The effect of changing the geometry of an intramolecular hydroxyl–hydroxyl H-bond on cooperativity with an intermolecular hydroxyl·quinuclidine H-bond was quantified by comparing the H-bonding properties of a series of hydroxycresols with the corresponding series of bisphenols. In the hydroxycresols, the intramolecular H-bond forms a 6-membered ring, and X-ray crystallography showed that the H-bond is distorted away from the ideal linear O–H⋯O geometry by up to 35°. In the bisphenols, the intramolecular H-bond forms an 8-membered ring, and the geometry is close to ideal, with the OH bond of the donor pointing directly at the lone pair of the acceptor. The presence of the intramolecular H-bonding interactions in solution was confirmed using ¹H NMR spectroscopy, and NMR titrations were used to measure the association constants for formation 1 : 1 complexes with quinuclidine in n-octane. Compared with the non-cooperative H-bond formed by benzyl alcohol with quinuclidine, the strength of the intermolecular H-bond formed by the hydroxycresols increased by between −8 kJ mol⁻¹ and −14 kJ mol⁻¹, depending on the substituent para to the phenol OH donor. Electron-withdrawing substituents make the phenol a better H-bond donor, and the increase in the strength of the intramolecular H-bond leads to an increase in the strength of the intermolecular H-bond with quinuclidine. For the bisphenols, the cooperative effects were very similar: the substituent effects were practically identical, and the presence of the intramolecular H-bond increased the strength of the intermolecular interaction by between −10 kJ mol⁻¹ and −16 kJ mol⁻¹. The results show that cooperativity in H-bonded networks depends strongly on the polarity of the interacting groups but is relatively insensitive to the precise geometric arrangement.