双-杂环卡宾配体保护的手性金纳米团簇的合成与对映体分离
Synthesis and enantioseparation of chiral Au nanoclusters protected by bis--heterocyclic carbene ligands.
作者信息
Yi Hong, Osten Kimberly M, Levchenko Tetyana I, Veinot Alex J, Aramaki Yoshitaka, Ooi Takashi, Nambo Masakazu, Crudden Cathleen M
机构信息
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University Furo Chikusa Nagoya 464-8602 Japan
Department of Chemistry, Queen's University Chernoff Hall Kingston Ontario K7L 3N6 Canada.
出版信息
Chem Sci. 2021 Jul 2;12(31):10436-10440. doi: 10.1039/d1sc03076k. eCollection 2021 Aug 11.
A series of chiral Au nanoclusters were synthesized the direct reduction of achiral dinuclear Au(i) halide complexes ligated by -xylyl-linked bis--heterocyclic carbene (NHC) ligands. A broad range of functional groups are tolerated as wingtip substituents, allowing for the synthesis of a variety of functionalized chiral Au nanoclusters. Single crystal X-ray crystallography confirmed the molecular formula to be [Au(bisNHC)Cl]Cl, with a chiral helical arrangement of the five bidentate NHC ligands around the icosahedral Au core. This Au nanocluster is highly luminescent, with a quantum yield of 23%. The two enantiomers of the Au clusters can be separated by chiral HPLC, and the isolated enantiomers were characterized by circular dichroism spectroscopy. The clusters show remarkable stability, including configurational stability, opening the door to further investigation of the effect of chirality on these clusters.
通过对由对二甲苯连接的双（杂环卡宾）（NHC）配体连接的非手性二核金（I）卤化物配合物进行直接还原，合成了一系列手性金纳米团簇。作为翼尖取代基，可以耐受多种官能团，从而能够合成各种功能化的手性金纳米团簇。单晶X射线晶体学证实分子式为[Au（双NHC）Cl]Cl，五个双齿NHC配体围绕二十面体金核呈手性螺旋排列。这种金纳米团簇具有高发光性，量子产率为23%。金团簇的两种对映体可以通过手性高效液相色谱法分离，分离出的对映体通过圆二色光谱进行表征。这些团簇表现出显著的稳定性，包括构型稳定性，为进一步研究手性对这些团簇的影响打开了大门。
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