The Interplay of Covalency, Hydrogen Bonding and Dispersion Leads to a Long Range Chiral Network: The Example of 2-Butanol

Abstract

The assembly of complex structures is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol shows interesting properties as a chiral modifier of surface chemistry, however, its mode of action is not fully understood. In order to probe its surface properties we employed high-resolution scanning tunneling microscopy and DFT simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations reveal that the tetramers are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. Our data reveals that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen bonds and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network's enantioselective interaction with other molecules.