The tetrahedral structure and luminescence properties of Bi-metallic Pt1Ag28(SR)18(PPh3)4 nanocluster.

The atomic-structure characterization of alloy nanoclusters (NCs) remains challenging but is crucial in order to understand the synergism and develop new applications based upon the distinct properties of alloy NCs. Herein, we report the synthesis and X-ray crystal structure of the Pt1Ag28(S-Adm)18(PPh3)4 nanocluster with a tetrahedral shape. Pt1Ag28 was synthesized by reacting Pt1Ag24(SPhMe2)18 simultaneously with Adm-SH (1-adamantanethiol) and PPh3 ligands. A tetrahedral structure is found in the metal framework of Pt1Ag28 NC and an overall surface shell (Ag16S18P4), as well as discrete Ag4S6P1 motifs. The Pt1Ag12 kernel adopts a face-centered cubic (FCC) arrangement, which is observed for the first time in alloy nanoclusters in contrast to the commonly observed icosahedral structure of homogold and homosilver NCs. The Pt1Ag28 nanocluster exhibits largely enhanced photoluminescence (quantum yield QY = 4.9%, emission centered at ∼672 nm), whereas the starting material (Pt1Ag24 NC) is only weakly luminescent (QY = 0.1%). Insights into the nearly 50-fold enhancement of luminescence were obtained via the analysis of electronic dynamics. This study demonstrates the atomic-level tailoring of the alloy nanocluster properties by controlling the structure.