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

Two ligand‐protected nanoscale silver moieties, [Ag 46 (SPhMe 2 ) 24 (PPh 3 ) 8 ](NO 3 ) 2 and [Ag 40 (SPhMe 2 ) 24 (PPh 3 ) 8 ](NO 3 ) 2 (abbreviated as Ag 46 and Ag 40 , 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 Ag 32 S 24 P 8 , which is reminiscent of fullerenes, and it encapsulates a well‐studied core, Ag 14 and a completely new core, Ag 8 , which correspond to a face‐centered cube and a simple cube, respectively, resulting in the Ag 46 and Ag 40 clusters. The presence of two entities (Ag 40 and Ag 46 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).