Angewandte Chemie - International Edition, vol.61, no.31, 2022 (SCI-Expanded)
© 2022 Wiley-VCH GmbH.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 [Ag155(CyS)40(TC4A)5Cl2] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p-tert-butylthiacalix[4]arene (H4TC4A). Its single-crystal structure consists of a metallic core of four concentric shells, Ag13@Ag42@Ag30@Ag70, lined with a organic skin of 40CyS− and 5TC4A4− 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.