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.