Thermal Stability and Electronic Properties of N-Heterocyclic Carbene-Protected Au13 Nanocluster and Phosphine-Protected Analogues.

Abstract

Despite significant advances in manufacturing atomically precise gold nanoclusters protected by various ligands, there is a limited understanding of the thermal stability dynamics and electronic properties of ligand effects. We conducted ab initio molecular dynamics (AIMD) simulations on the well-characterized [Au13(NHCMe)9Cl3]2+ nanocluster and its counterpart [Au13(PMe3)9Cl3]2+ cluster to evaluate the thermal stability induced by N-heterocyclic carbene (NHC) and phosphine ligands. The result shows that under vacuum conditions, [Au13(PMe3)9Cl3]2+ is more stable than [Au13(NHCMe)9Cl3]2+, and both lead to metal nucleation decomposition, breaking into the Au12 fragment and L-Au-Cl (L = NHCMe or PMe3) complexes eventually. The optical and electronic properties of these two clusters change significantly due to ligand alteration. Furthermore, we have designed a novel [Au13(NHCMe)(PMe3)8Cl3]2+ cluster coprotected by NHC and phosphine ligands, displaying higher thermal stability than the homoligand protected [Au13(NHCMe)9Cl3]2+ and [Au13(PMe3)9Cl3]2+. Our hypothetical species are an interesting model for nanostructured materials, facilitating the experimental exploration of cluster synthesis and catalytic applications.