Dynamics of weak interactions in the ligand layer of meta-mercaptobenzoic acid protected gold nanoclusters Au68(m-MBA)32 and Au144(m-MBA)40

Atomically precise metal nanoclusters, stabilized and functionalized by organic ligands, are emerging nanomaterials with potential applications in plasmonics, nano-electronics, bio-imaging, nanocatalysis, and as therapeutic agents or drug carriers in nanomedicine. The ligand layer has an important role in modifying the physico-chemical properties of the clusters and in defining the interactions between the clusters and the environment. While this role is well recognized from a great deal of experimental studies, there is very little theoretical information on dynamical processes within the layer itself. Here, we have performed extensive molecular dynamics simulations, with forces calculated from the density functional theory, to investigate thermal stability and dynamics of the ligand layer of the meta-mercaptobenzoic acid (m-MBA) protected Au-68 and Au-144 nanoclusters, which are the first two gold nanoclusters structurally solved to atomic precision by electron microscopy [Azubel et al., Science, 2014, 345, 909 and ACS Nano, 2017, 11, 11866]. We visualize and analyze dynamics of three distinct non-covalent interactions, viz., ligand-ligand hydrogen bonding, metal-ligand O = C-OHMIDLINE HORIZONTAL ELLIPSISAu interaction, and metal-ligand Ph(pi)MIDLINE HORIZONTAL ELLIPSISAu interaction. We discuss their relevance for defining, at the same time, the dynamic stability and reactivity of the cluster. These interactions promote the possibility of ligand addition reactions for bio-functionalization or allow the protected cluster to act as a catalyst where active sites are dynamically accessible inside the ligand layer.