Shen Hui, Xu Zhen, Wang Lingzheng, Han Ying-Zi, Liu Xianhu, Malola Sami, Teo Boon K, Häkkinen Hannu, Zheng Nanfeng
State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, 40014, Jyväskylä, Finland.
Angew Chem Int Ed Engl. 2021 Oct 4;60(41):22411-22416. doi: 10.1002/anie.202108141. Epub 2021 Sep 1.
We report the synthesis and structure of tertiary chiral nanostructures with 100 % optical purity. A novel synthetic strategy, using chiral reducing agent, R and S-BINAPCuBH (BINAP is 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl), is developed to access to atomically precise, intrinsically chiral [Au Ag Cu (R- or S-BINAP) (SCH Ph) ]SbF nanoclusters in one-pot synthesis. The clusters represent the first tri-metallic superatoms with inherent chirality and fair stability. Both metal distribution (primary) and ligand arrangement (secondary) of the enantiomers exhibited perfect mirror images, and unprecedentedly, the self-assembly driven by the C-H⋅⋅⋅F interaction between the phenyl groups of the superatom moieties and SbF anions induced the formation of bio-mimic left- and right-handed helices, achieving the tertiary chiral nanostructures. DFT calculations revealed the connections between the molecular details and chiral optical activity.
我们报道了具有100%光学纯度的手性三级纳米结构的合成与结构。开发了一种使用手性还原剂R和S-BINAPCuBH（BINAP为2,2'-双（二苯基膦基）-1,1'-联萘）的新型合成策略，通过一锅法合成获得原子精确、具有固有手性的[Au Ag Cu (R-或S-BINAP) (SCH Ph) ]SbF纳米团簇。这些团簇代表了首批具有固有手性和良好稳定性的三金属超原子。对映体的金属分布（一级）和配体排列（二级）均呈现出完美的镜像，而且前所未有的是，超原子部分的苯基与SbF阴离子之间的C-H⋅⋅⋅F相互作用驱动的自组装诱导形成了仿生左手和右手螺旋，从而实现了手性三级纳米结构。密度泛函理论计算揭示了分子细节与手性光学活性之间的联系。
