Cooperativity in a cycloalkane-1,2/1,3-polyol corona: Topological hydrogen bonding in 1,2-diol motifs

A corona, consisting of 18 carbon atoms bearing 12 hydroxy groups in a continuous hydrogen-bonded chain, is built up by alternating degenerate conformations of alternating alkane-1,2-diol and 1,3-diol motifs. Geometries, proton nuclear magnetic resonance shifts and interaction energies for the dodecahydroxycyclo-octadecane and selected fragments are determined by density functional calculations at the B3LYP/6-311+G(d,p) level. Cooperative effects of O–H?O–H bonding are evident from the simple juxtaposition of these two motifs with a common OH group in butane-1,2,4-triol conformers. Bracketing a 1,2-diol motif with two 1,3-diol motifs in hexane-1,3,4,6-tetrol leads to a structure in which the 1,2-diol motif displays a bond critical point for hydrogen bonding. This is associated with enhancement of the shift of the hydrogen-bonded OH proton and of the corresponding H?O interaction energy. The full corona has a complete outer ring of O–H?O–H bond paths, and an inner ring of bond paths, due to C–H?H–C hydrogen–hydrogen bonding, which result in a central ring critical point. The topological O–H?O–H hydrogen bond, never seen in simple alkane-1,2-diols, is associated with cooperative enhancement of the H?O interaction energy, but this is not a necessary condition for a bond path: values for topological C–H?H–C hydrogen–hydrogen bonds can be as low as ?0.4 kcal mol^?1.