title: Thiacalix[4]arene: New protection for metal nanoclusters.
abstract: Surface organic ligands are critical for the formation and properties of atomically precise metal nanoclusters. In contrast to the conventionally used protective ligands such as thiolates and phosphines, thiacalix[4]arene has been used in the synthesis of a silver nanocluster, [Ag35(H2L)2(L)(C≡CBu(t))16](SbF6)3, (H4L, p-tert-butylthiacalix[4]-arene). This is the first structurally determined calixarene-protected metal nanocluster. The chelating and macrocyclic effects make the thiacalix[4]arene a rigid shell that protects the silver core. Upon addition or removal of one silver atom, the Ag35 cluster can be transformed to Ag36 or Ag34 species, and the optical properties are changed accordingly. The successful use of thiacalixarene in the synthesis of well-defined silver nanoclusters suggests a bright future for metal nanoclusters protected by macrocyclic ligands.
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Zong-Jie
authors.identifier: 0000-0001-8977-0850
authors.initials: ZJ
authors.lastname: Guan
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Jiu-Lian
authors.identifier: 1595-9263-7351-2345
authors.initials: JL
authors.lastname: Zeng
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Zi-Ang
authors.identifier: 0000-0003-0635-9789
authors.initials: ZA
authors.lastname: Nan
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Xian-Kai
authors.initials: XK
authors.lastname: Wan
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Yu-Mei
authors.initials: YM
authors.lastname: Lin
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.; Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
authors.forename: Quan-Ming
authors.initials: QM
authors.lastname: Wang
mesh_terms: D008024:Ligands; D053768:Metal Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D008958:Models, Molecular; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry*; D012834:Silver / Q000737:chemistry; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry*
chemical_list: D008024:Ligands; D010636:Phenols; D013440:Sulfides; C500450:thiacalix(4)arene; D012834:Silver
keywords: Calixarene; alkynyl ligand; coordination mode; crystal structure; ligand-protected metal nanocluster; silver nanocluster