Three Silver Nests Capped by Thiolate/Phenylphosphonate

Introducing phenylphosphonic acid (H2PPA) 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 Ag9S2 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 H2PPA strongly influences the structures of silver thiolate nests, thus providing a new route to fabricate and modify them in a more rational way. A place to call home: Introducing phenylphosphonic acid into the Ag/tBuSH assembly system has led to a family of nanoscale‐sized high‐nuclearity silver thiolate/PPA nests (see figure) with impressive core–shell features, the core and shell structures consisting of Ag9S2@Ag36, Ag20@Ag44, and Ag@Ag24@Ag48 clusters. Two of the nests luminesce in the NIR region and show different luminescent thermochromic behavior.