Intramolecular Hydrogen Bond Energy and Cooperative Interactions in α-, β-, and γ-Cyclodextrin Conformers

Accurate estimation of individual intramolecular hydrogen bond (H-bond) energies is an intricate task for multiply H-bonded systems. In such cases, the hydrogen bond strengths could be highly influenced by the cooperative interactions, for example, those between hydroxyl groups in sugars. In this work, we use the recently proposed molecular tailoring approach-based quantification (Deshmukh, Gadre, and Bartolotti, J Phys Chem A 2006, 110, 12519) to the extended systems of cyclodextrins (CDs). Further, the structure and stability of different conformers of alpha-, beta-, and gamma-CDs are explained based on the energetics and cooperative contribution to the strength of these H-bonds. The estimated O-H center dot center dot center dot O H-bond energies in the various CD conformers are found to vary widely from 1.1 to 8.3 kcal mol(-1). The calculated energy contributions to cooperativity toward the H-bond strengths fall in the range of 0.25-2.75 kcal mol(-1). (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 2996-3004, 2011