A luminescent Ag 8 (DPPY) 6 (PhCC) 6 cluster with a triangular superatomic Ag 8 core.

We have synthesized single crystals of a highly stable Ag 8 nanocluster protected by six ligands of diphenyl-2-phosphinic pyridine (DPPY) plus six ligands of phenylacetylene (PhCC). This Ag 8 (DPPY) 6 (PhCC) 6 cluster bears a triangular superatomic Ag 8 core, with the vertex and edge Ag atoms (quasi-triangle Ag 6 ) being protected by both P and N bidentate coordination of the six DPPY ligands; meanwhile, the six PhCC ligands via μ 3 -C coordination form coordination on the two central Ag atoms capped on both sides of the triangle facet. Apart from the well-organized coordination of the two ligands pertaining to the balanced interactions with the Ag 8 core, this Ag 8 nanocluster exhibits superatomic stability with two delocalized valence electrons (1S 2 ||1P 0 ), assuming that the six PhCC ligands fix 6 localized electrons from the Ag atoms. Interestingly, the Ag 8 (DPPY) 6 (PhCC) 6 NCs display temperature-dependent dual emissions at 330 and 535 nm under deep ultraviolet excitation. TD-DFT calculations reproduced the experimental spectrum, shedding light on the nature of excitation states and metal-ligand interactions in such a superatomic metal cluster.