Three Silver Nests Capped by Thiolate/Phenylphosphonate

Introducing phenylphosphonic acid (H 2 PPA) into the Ag/ t BuSH assembly system has produced a family of nanoscale‐sized, high‐atom number, silver thiolate/PPA nests ( SD/Ag45 a , SD/Ag66 a , and SD/Ag73 a ) with impressive core–shell features. SD/Ag45 a is a 45‐atom ellipsoid comprised of an Ag 36 shell trapping an Ag 9 S 2 three‐bladed rotor inside. SD/Ag66 a comprises an inner rod‐like Ag 20 core and an outer Ag 44 shell, giving a 64‐atom nest. These Ag 64 nests are further extended by Ag(CN) 2 linkers to form a one‐dimensional chain structure. SD/Ag73 a is a three‐shell 73‐nucleus silver nest with a central silver atom enclosed in a rhombicuboctahedron of 24 silver atoms, which is itself enclosed in the outermost shell of a rectified version of a 48‐Ag octahedral Goldberg 2,0 cage. The solution behaviors and optical absorption properties of the three nests are described in detail. Of note, SD/Ag45 a and SD/Ag73 a emit in the near‐infrared region and show different luminescent thermochromic behavior. This work demonstrates that the participation of H 2 PPA strongly influences the structures of silver thiolate nests, thus providing a new route to fabricate and modify them in a more rational way.