ESI-MS Identification of the Cationic Phosphine-Ligated Gold Clusters Au1-22: Insight into the Gold-Ligand Ratio and Abundance of Larger Clusters

Abstract

Triphenylphosphine (PPh₃)-ligated gold nanoclusters are valuable for a number of potential applications due to their relative ease of synthesis and usefulness in forming advanced cluster architectures. While previous studies have reported cationic PPh₃-ligated gold clusters with core sizes of Au_1-4, Au_6-11, and Au_13-14, there has not been definitive identification by mass spectrometry of many larger clusters in the Au_12-25 range. Herein, we survey a polydisperse solution of cationic PPh₃-ligated gold clusters using high-mass-resolution (M/ΔM = 60,000) electrospray ionization mass spectrometry (ESI-MS). To improve the sensitivity and mass resolution of larger clusters for unambiguous identification, we increased the number of scan averages and reduced the range of mass collection windows to 200 m/z, thereby mitigating potential mass and ion abundance bias resulting from smaller "building block" gold clusters that are present in much higher abundance in solution. In addition to the previously reported clusters, we identify several new species including Au₅(PPh₃)₅⁺, Au₁₂(PPh₃)₉HCl²⁺, Au₁₅(PPh₃)₉Cl²⁺, Au₁₆(PPh₃)₁₀Cl₂²⁺, Au₁₇(PPh₃)₁₁³⁺, Au₁₈(PPh₃)₁₀²⁺, Au₁₉(PPh₃)₁₀Cl²⁺, Au₂₀(PPh₃)₁₂H₃³⁺, Au₂₁(PPh₃)₁₀Cl²⁺, and Au₂₂(PPh₃)₁₀Cl₂²⁺, indicating that a full range of clusters between Au_1-22 may be observed in a single polydisperse solution. Considering all of the clusters observed, our findings provide evidence that the Au_12-14 size range is a critical transition point in cluster nucleation. While smaller clusters exhibit a 1:1 gold-to-ligand ratio, larger clusters (beginning Au_12-14) feature additional gold atoms without an equal number of accompanying ligands. Our results support previous evidence in the literature indicating that the "magic number" icosahedral Au₁₃ geometry is the smallest cluster size where a ligand-less central gold atom is coordinated by a complete shell of 12 surrounding ligated gold atoms, thereby creating a stable "one-shell" cluster. Furthermore, our findings reinforce growing evidence that ligands may be used to actively direct gold cluster size and abundance during synthesis. While for PPh₃-ligated systems the most abundant species are Au_6-9 clusters, we find that for related methyldiphenylphosphine (PPh₂Me) and dimethylphenylphosphine (PPhMe₂)-ligated systems the most abundant cluster sizes are Au_10-11 and Au_12-14, respectively. Together, we demonstrate that reducing the range of m/z collection windows and increasing the number of scan averages dramatically improves instrument sensitivity for cationic gold clusters, enabling thorough characterization of polydisperse solutions that is not possible using conventional techniques.