An Ultrastable 155‐Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion

Abstract Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed‐valence silver nanocluster [Ag 155 (CyS) 40 (TC4A) 5 Cl 2 ] ( Ag155 ) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p ‐ tert ‐butylthiacalix[4]arene (H 4 TC4A). Its single‐crystal structure consists of a metallic core of four concentric shells, Ag 13 @Ag 42 @Ag 30 @Ag 70 , lined with a organic skin of 40CyS − and 5TC4A 4− and 2Cl − . Ag155 manifests an unusual pseudo‐5‐fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.