Amplification of chirality in surface-confined supramolecular bilayers

Nature Communications
Hai Cao, Steven De Feyter

Abstract

One of the most dramatic effects of supramolecular assembly is the generation of homochirality in near-racemic systems. It is normally infeasible though to flip the absolute chirality of a molecule. Here we rationalize this seemingly contradictory chiral amplification mechanism with a combined scanning tunneling microscopy (STM) and modeling study of surface-grown enantiomerically unbalanced supramolecular bilayers. We identify a chemical equilibrium between opposite but not mirror-image-related twisting molecular geometries of the pure enantiomer, and accordingly two competing aggregation pathways. The nonlinear chiral amplification effect in bilayers of near-racemic mixtures involves the biased adsorption and organization of the majority enantiomer, and the compliance of the minority enantiomer to adopt an energetically less favorable twisting molecular conformation and handed organization. By establishing a direct link between molecular building block architectures and chiral amplification effect, this study provides a general approach to gain insight into cooperative supramolecular assembly in mixed enantiomer systems.

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Citations

Nov 24, 2020·Chemistry : a European Journal·Minggao QinChuanliang Feng
Jun 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Mingliang GuiFeng Wang
Jan 1, 2021·ACS Applied Materials & Interfaces·Qiuhong ChengPengyao Xing
Apr 21, 2020·Journal of the American Chemical Society·Yuan FangYoshito Tobe
Feb 25, 2020·ACS Applied Materials & Interfaces·Sasan ShadpourTorsten Hegmann
Jan 7, 2020·Journal of the American Chemical Society·Simin ZhangXun Wang
Sep 23, 2021·Physical Chemistry Chemical Physics : PCCP·Mykola TelychkoJiong Lu

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Methods Mentioned

BETA
scanning tunneling microscopy
column chromatography

Software Mentioned

Scanning Probe Image Processor
Gaussian
Castep
Image Metrology ApS

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