Zeng Chenjie, Jin Rongchao
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, 15213, USA.
Chem Asian J. 2017 Aug 4;12(15):1839-1850. doi: 10.1002/asia.201700023. Epub 2017 Jun 27.
Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au (SR) ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au (SR) structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au (SR) and Au (SR) nanoclusters. Overall, the origins of chirality discovered in Au (SR) nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles.
手性纳米材料在许多领域都引起了广泛关注,但在许多情况下,原子水平上手性的确切起源仍然难以捉摸。随着原子精确的金纳米团簇(例如硫醇盐保护的Au(SR))最近取得的重大进展,基于使用单晶X射线晶体学确定的原子结构,已经揭示了几种手性起源。报道的手性Au(SR)结构明确揭示了手性的一个主要起源,它来自金属-配体界面处的Au-S手性模式,这与内芯(即内核)中金属原子的手性排列相反。此外,手性配体也可以引入手性,表现为除配体自身跃迁之外的基于金属的电子跃迁的圆二色性响应。最后,在最近关于手性Au(SR)和Au(SR)纳米团簇的一项工作中,还发现了配体碳尾的手性排列。总体而言,在Au(SR)纳米团簇中发现的手性起源可能为理解其他类型纳米材料中的手性起源提供模型,也构成了开发手性纳米粒子各种应用的基础。