Phosphine-Ligated Gold Clusters with Core+ exo Geometries: Unique Properties and Interactions at the Ligand-Cluster Interface.

Over recent years, research on the structures and properties of ligand-protected gold cluster molecules has gained significant interest. The crystal structure information accumulated to date has revealed the structural preference to adopt closed polyhedral geometries, but the use of multidentate ligands sometimes leads to the formation of exceptional structures. This Account describes results of our studies on diphosphine-coordinated [core+ exo]-type gold clusters featuring extra gold atoms outside the polyhedral cores, highlighting (1) their distinct optical properties due to the unique electronic structures generated by the exo gold atoms and (2) electronic/attractive ligand-cluster interactions that cause definite perturbation effects on the cluster properties. Subnanometer gold clusters with [core+ exo]-type geometries (nuclearity = 6, 7, 8, and 11) commonly displayed single absorption bands in the visible region, which are distinct in patterns from those of conventional polyhedral-only homologues. Theoretical studies demonstrated that the exo gold atoms are critically involved in the generation of unique electronic structures characterized by the HOMO-LUMO transitions with dominant oscillator strengths, leading to the appearance of the isolated absorption bands. On the basis of the frontier orbital distributions, the HOMO and LUMO were shown to be localized around the polyhedral cores and exo gold atoms, respectively. Therefore, the HOMO-LUMO transitions responsible for the visible absorptions occur in the core → exo direction. The HOMO-LUMO gap energies showed no clear trends with respect to the nuclearity (size), indicating that the individual geometric features of the inorganic framework primarily govern the clusters' electronic structures and properties. Systematic studies using octagold clusters bearing various anionic coligands revealed that electronic or attractive interactions between the gold framework and ligand functionalities, such as π-electron systems and heteroatoms, cause substantial perturbations of the wavelength of the visible absorption band due to the HOMO-LUMO transitions. Especially, significant red shifts were observed as a result of the electronic coupling with specific π-resonance contributors. It was also found that the orientation of aromatic rings around the inorganic framework is a factor that affects the cluster photoluminescence. These findings demonstrate the utility of the ligand moieties surrounding the gold frameworks for fine-tuning of the optical properties. During these studies, unusual but definite attractive interactions between the gold framework and C-H groups of the diphosphine ligand were found in the hexagold clusters. On the basis of careful crystallographic and NMR analyses, these interactions were deemed as a certain kind of M···H hydrogen bonds, which critically affect the maintenance of the cluster framework. Such unique interaction activities are likely due to the valence electrons in the gold framework, which serve as the hydrogen-bond acceptor for the unfunctionalized C-H groups. Overall, these observations imply the uniqueness of the ligand-cluster interface associated with the partially oxidized gold entities, which may expand the scope of ligand-protected clusters toward various applications.