Thiacalix[4]arene: New protection for metal nanoclusters.
Thiacalix[4]arene: New protection for metal nanoclusters.
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Thiacalix[4]芳烃：金属纳米团簇的新保护
DOI：
10.1126/sciadv.1600323
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发表时间：
2016-08
期刊：
影响因子：
13.6
通讯作者：
Wang QM
中科院分区：
文献类型：
--
作者：
Guan ZJ;Zeng JL;Nan ZA;Wan XK;Lin YM;Wang QM
有机大环配体在精确控制银纳米团簇的结构和光学性质方面具有广阔的应用前景。表面有机配体对于原子精密金属纳米团簇的形成和性质是至关重要的。与传统使用的硫酸盐和膦保护配体不同，硫杂杯[4]芳烃被用于合成银纳米簇合物[Ag35(H_2L)_2(L)(C-≡C But)16](SbF_6)_3，(H_4L，对叔丁基硫杂杯[4]-芳烃)。这是第一个结构确定的杯芳烃保护的金属纳米簇。螯合和大环效应使硫代杯[4]芳烃成为保护银核的坚硬外壳。当添加或移除一个银原子时，Ag35团簇可以转变为Ag36或Ag34物种，光学性质也相应改变。硫代杯芳烃在合成结构清晰的银纳米团簇中的成功应用，预示着大环配体保护的金属纳米团簇具有广阔的应用前景。
An organic macrocycle ligand is promising in precisely controlling the structures and optical properties of silver nanoclusters. 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≡CBut)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.