The molecular structure and intermolecular interactions of 1,3:2,4-dibenzylidene-D-sorbitol

The 1,3(R):2,4(S)-dibenzylidene-D-sorbitol (DBS) molecule is a low molar mass organic gelator (LMOG) that is capable of hydrogen-bonding with itself. As a consequence, DBS molecules self-organize into nanofibrillar networks at relatively low concentrations in a wide variety of organic solvents and polymers. In this work, molecular mechanics and molecular dynamics simulations were conducted to elucidate the equilibrium structure of DBS and the molecular interactions that govern DBS self-assembly. Molecular mechanics calculations performed on single DBS molecules with Cerius2 and InsightII software reveal that the phenyl rings tend to adopt an equatorial position and that the pendant hydroxyl group prefers to form an intramolecular hydrogen bond with an acetal oxygen, in contrast to the terminal hydroxyl group. Molecular mechanics and molecular dynamics on DBS dimers reveal that they are capable of forming hydrogen bonds and participating in π interactions, suggesting that the mechanism of nanofibrillar network formation may be complex, involving more than one type of physical interaction.