Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)(24)](4-) Nanoclusters via Ion Pairing

作者：Yan, Juanzhu; Su, Haifeng; Yang, Huayan; Hu, Chengyi; Malola, Sami; Lin, Shuichao; Teo, Boon K.^*; Hakkinen, Hannu; Zheng, Nanfeng^*

来源：Journal of the American Chemical Society, 2016, 138(39): 12751-12754.

DOI：10.1021/jacs.6b08100

• OPTICAL-ACTIVITY
• GOLD CLUSTERS
• CHIROPTICAL PROPERTIES
• CIRCULAR-DICHROISM
• METAL NANOCLUSTERS
• SURFACE LIGANDS
• NANOPARTICLES
• THIOLATE
• SEPARATION
• AU-38

In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric shell cluster, [Ag28Cu12(SR)(24)](4-), was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymmetric synthesis of optically active enantiomers of [Ag28Cu12(SR)(24)](4-) was achieved by using appropriate chiral ammonium cations (such as N-benzylcinchoninium vs N-benzylcinchonidinium) in the cluster synthesis. These simple strategies, ion pairing enantioseparation and direct asymmetric synthesis using chiral counterions, may be of general use in preparing chiral metal nanoparticles.

• 出版日期2016-10-5
• 单位厦门大学