Three Silver Nests Capped by Thiolate/Phenylphosphonate.

Introducing phenylphosphonic acid (H2 PPA) into the Ag/tBuSH 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 Ag36 shell trapping an Ag9 S2 three-bladed rotor inside. SD/Ag66 a comprises an inner rod-like Ag20 core and an outer Ag44 shell, giving a 64-atom nest. These Ag64 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 H2 PPA strongly influences the structures of silver thiolate nests, thus providing a new route to fabricate and modify them in a more rational way.