Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Abstract

Two ligand-protected nanoscale silver moieties, [Ag₄₆ (SPhMe₂ )₂₄ (PPh₃ )₈ ](NO₃ )₂ and [Ag₄₀ (SPhMe₂ )₂₄ (PPh₃ )₈ ](NO₃ )₂ (abbreviated as Ag₄₆ and Ag₄₀ , respectively) with almost the same shell but different cores were synthesized simultaneously. As their external structures are identical, the clusters were not distinguishable and become co-crystallized. The occupancy of each cluster was 50 %. The outer shell of both is composed of Ag₃₂ S₂₄ P₈ , which is reminiscent of fullerenes, and it encapsulates a well-studied core, Ag₁₄ and a completely new core, Ag₈ , which correspond to a face-centered cube and a simple cube, respectively, resulting in the Ag₄₆ and Ag₄₀ clusters. The presence of two entities (Ag₄₀ and Ag₄₆ clusters) in a single crystal and their molecular formulae were confirmed by detailed electrospray ionization mass spectrometry. The optical spectrum of the mixture showed unique features which were in good agreement with the results from time-dependent density functional theory (TD-DFT).