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Tertiary Chiral Nanostructures from C−H⋅⋅⋅F Directed Assembly of Chiroptical Superatoms
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2021-08-04 , DOI: 10.1002/anie.202108141
Hui Shen 1 , Zhen Xu 1 , Lingzheng Wang 1 , Ying-Zi Han 1 , Xianhu Liu 1 , Sami Malola 2 , Boon K Teo 1 , Hannu Häkkinen 2 , Nanfeng Zheng 1
Affiliation  

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-BINAPCuBH4 (BINAP is 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl), is developed to access to atomically precise, intrinsically chiral [Au7Ag6Cu2(R- or S-BINAP)3(SCH2Ph)6]SbF6 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 SbF6 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.

中文翻译:

来自手性超原子的 C−H⋅⋅⋅F 定向组装的三次手性纳米结构

我们报告了具有 100% 光学纯度的三级手性纳米结构的合成和结构。开发了一种使用手性还原剂 R 和 S-BINAPCuBH 4(BINAP 是 2,2'-Bis(diphenylphosphino) -1,1'-binaphthyl)的新型合成策略,以获取原子级精确的本征手性 [Au 7 Ag 6 Cu 2 (R-或S-BINAP) 3 (SCH 2 Ph) 6 ]SbF 6一锅合成中的纳米团簇。这些簇代表了第一个具有固有手性和相当稳定性的三金属超原子。对映异构体的金属分布(主要)和配体排列(次要)都表现出完美的镜像,并且前所未有地,由超原子部分的苯基和 SbF 6 -之间的 CH⋅⋅⋅F 相互作用驱动的自组装阴离子诱导仿生左手和右手螺旋的形成,实现了三级手性纳米结构。DFT 计算揭示了分子细节和手性光学活性之间的联系。
更新日期:2021-09-27
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