Different Silver Nanoparticles in One Crystal: Ag₂₁₀(iPrPhS)₇₁(Ph₃P)₅Cl and Ag₂₁₁(iPrPhS)₇₁(Ph₃P)₆Cl

Two pure silver nanoparticles (Ag 210 ( i PrPhS) 71 (Ph 3 P) 5 Cl and Ag 211 ( i PrPhS) 71 (Ph 3 P) 6 Cl labeled as SD/Ag210 and SD/Ag211 (SD=SunDi), were found to co‐crystallize in forming compound 1 . Single‐crystal X‐ray diffraction (SCXRD) revealed that they differ by only one Ag(PPh 3 ). Their four‐shell nanoparticles consist of three pure Ag metal shells (Ag 19 @Ag 52 @Ag 45 ) shielded by a silver‐organic Ag 89 ( i PrPhS) 71 Cl[Ag(Ph 3 P)] n outermost shell. The number ( n ) of Ag(Ph 3 P) is five for SD/Ag210 and six for SD/Ag211. The pseudo‐fivefold symmetric Ag nanoparticles exhibit surface plasmon absorption similar to a true metallic state but at the nanoscale. This work exemplifies the important effects of phosphine in stabilizing large silver nanoparticles; and offers a platform to investigate the origin of differences in nanoscale metal materials, even differing by only one metal atom; it also sheds light on the regioselective binding of auxiliary Ph 3 P on the surface of silver nanoparticles.