硫杂杯[4]芳烃：金属纳米团簇的新保护剂。
Thiacalix[4]arene: New protection for metal nanoclusters.
机构信息
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
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.
出版信息
Sci Adv. 2016 Aug 12;2(8):e1600323. doi: 10.1126/sciadv.1600323. eCollection 2016 Aug.
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))163, (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.
表面有机配体对于原子精确金属纳米团簇的形成和性质至关重要。与传统使用的保护配体（如硫醇盐和膦）相比，硫代杯[4]芳烃已被用于合成银纳米团簇Ag35(H2L)2(L)(C≡CBu(t))163（H4L，对叔丁基硫代杯[4]-芳烃）。这是第一个结构确定的杯芳烃保护的金属纳米团簇。螯合和大环效应使硫代杯[4]芳烃成为刚性壳，保护银核。加入或除去一个银原子后，Ag35 团簇可以转化为 Ag36 或 Ag34 物种，并且光学性质相应地发生变化。硫代杯芳烃在合成具有明确结构的银纳米团簇中的成功应用表明，大环配体保护的金属纳米团簇具有广阔的前景。
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