Chiral functionalization of solid surfaces with amino acid derivatives: diazonium grafting regulated by enantioselective processes

Abstract

Chiral inorganic nanostructures are essential for many enantioselective processes. It is possible to bestow chirality on otherwise achiral inorganic materials, via covalent functionalization of their surfaces with chiral organic molecules. However, controlling the degree of covalent functionalization is challenging, and there is an urgent need to find new avenues that can be applied to attach chiral moieties on different types of surfaces. By taking advantage of the versatility of diazonium chemistry, here we present a combined SPM/Raman study of the covalent grafting of amino acid-derived molecules on two different solid surfaces, with the intention to evaluate the effect of chiral reductants, chirally functionalized surfaces and chiral solvents on the chiral functionalization of solid surfaces. We show that the all three chiral species have an effect on the grafting of amino acid derivatives on solid surfaces, but affect the covalent attachment in different fashions. With a survey of the different aspects at play in chiral functionalization of solid surfaces, this study may offer a potential solution for the controlled production of many chiral nanostructures, and might also shine some light on the understanding of enantiospecific processes on inorganic crystalline surfaces.