Wang, ZhiAlkan, FahriAikens, Christine M.Kurmoo, MohamedallyZhang, Zhen-YiSong, Ke-PengSun, Di2025-09-252025-09-2520221521-37731433-7851https://doi.org/10.1002/anie.202206742https://hdl.handle.net/20.500.12573/3268Sun, Di/0000-0001-5966-1207; Alkan, Fahri/0000-0002-4046-9044; Wang, Zhi/0000-0001-8315-3501;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.eninfo:eu-repo/semantics/closedAccessC-5H SymmetryEsi-MsPhotothermal ConversionSilver NanoclusterThiacalix[4]ArenesC5h SymmetryArticle10.1002/anie.2022067422-s2.0-85131884229