Total Structure Determination of the Pt₁Ag₉[P(Ph‐F)₃]₇Cl₃ Nanocluster

Abstract

An atomically precise luminescent Pt‐Ag alloy nanocluster (Pt1Ag9[P(Ph‐F)3]7Cl3 (P(Ph‐F)3= tris(4‐fluorophenyl) phosphine)) (Pt1Ag9 for short) was synthesized. Its structure was determined by single‐crystal X‐ray diffraction (SCXRD) and further confirmed by electrospray ionization mass spectrometry (ESI‐MS), X‐ray photoelectron spectrospray (XPS) and Nuclear Magnetic Resonance (NMR) measurements. Surprisingly, the Pt1Ag9 kernel can be regarded as the icosahedral Pt1Ag12 kernel missing three Ag atoms, accompanied with no structural reformation in this nanocluster. And the central Pt atom was exposed and capped by phosphine ligand directly in contrast with other reported Pt‐Ag alloy nanoclusters. Upon excitation at 435 nm, the emission spectra of Pt1Ag9 nanocluster exhibits a prominent peak at 662 nm (quantum yield QY = 0.6658 %) with a very short photoluminescence lifetime (0.357 ns). This work provides a deep understanding of the structure and properties of Pt‐Ag alloy nanoclusters.

One-step preparation of Pt/Ag nanoclusters for CO2 transformation

“…Of note, a similar structure of Pt 1 Ag 9 [P(Ph-F) 3 ] 7 Cl 3 has been reported by Zhu et al , in which the average bond lengths of Pt–Ag and Ag–Ag are 2.747 and 2.873 Å, respectively. 69 Both values of Pt 1 Ag 9 [P(Ph-F) 3 ] 7 Cl 3 are slightly larger than those of PtAg 9 described in this work, suggesting the stronger interaction of the atoms in title PtAg 9 . We note that the differences in bond lengths between the two structures have a significant effect on their physicochemical properties, such as stability ( vide infra ).…”