Computational Insight into the Covalent Organic–Inorganic Interface

From chemical functionalization of an inorganic substrate to protection/passivation of a nanocluster/nanoparticle surface, the organic–inorganic interface is key to chemistry of many materials. Herein computational insights into the structure, bonding, and energetics of several representative covalent organic–inorganic interfaces are reviewed mainly from the authors’ work and based on density functional theory. We start with the zero-curvature substrates including graphene, metal surfaces, and MoS 2 and discuss their covalent functionalization by the attachment of the aryl group via the diazonium chemistry. We then move on to large-curvature, ligand-protected gold nanoclusters where we focus on the ligand–gold interface. The theoretical studies have produced both general trends that help understand the experimental results and specific predictions that have been confirmed or are yet to be verified. Opportunities abound in coupling theory and experiment to understand the roles of the covalent organic–inorganic interfaces in synthesis and application of nanomaterials.