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Amplification of chirality in two-dimensional enantiomorphous lattices

Nature volume 439, pages 449–452 (2006)Cite this article

Abstract

The concept of chirality dates back to 1848, when Pasteur manually separated left-handed from right-handed sodium ammonium tartrate crystals1. Crystallization is still an important means for separating chiral molecules into their two different mirror-image isomers (enantiomers)2, yet remains poorly understood3. For example, there are no firm rules to predict whether a particular pair of chiral partners will follow the behaviour of the vast majority of chiral molecules and crystallize together as racemic crystals4, or as separate enantiomers. A somewhat simpler and more tractable version of this phenomenon is crystallization in two dimensions, such as the formation of surface structures by adsorbed molecules. The relatively simple spatial molecular arrangement of these systems makes it easier to study the effects of specific chiral interactions5; moreover, chiral assembly and recognition processes can be observed directly and with molecular resolution using scanning tunnelling microscopy6,7,8,9. The enantioseparation of chiral molecules in two dimensions is expected to occur more readily because planar confinement excludes some bulk crystal symmetry elements and enhances chiral interactions10,11; however, many surface structures have been found to be racemic12,13,14,15,16,17,18. Here we show that the chiral hydrocarbon heptahelicene on a Cu(111) surface does not undergo two-dimensional spontaneous resolution into enantiomers19, but still shows enantiomorphism on a mesoscopic length scale that is readily amplified. That is, we observe formation of racemic heptahelicene domains with non-superimposable mirror-like lattice structures, with a small excess of one of the heptahelicene enantiomers suppressing the formation of one domain type. Similar to the induction of homochirality in achiral enantiomorphous monolayers20 by a chiral modifier, a small enantiomeric excess suffices to ensure that the entire molecular monolayer consists of domains having only one of two possible, non-superimposable, mirror-like lattice structures.

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Figure 1: Enantiomorphous domains of racemic heptahelicene on Cu(111).
Figure 2: Identification of enantiomeric composition.
Figure 3: Nonlinear amplification of chirality in non-racemic layers.
Figure 4: Illustration of the energetic contributions driving the chiral amplification mechanism.

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Acknowledgements

This work was supported by the Swiss National Science Foundation (SNF). We thank O. Gröning for writing the software to simulate STM images and U. Ellerbeck for the [7]H synthesis.

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Authors and Affiliations

  1. Empa, Swiss Federal Laboratories for Materials Testing and Research, Überlandstrasse 129, CH-8600, Dübendorf, Switzerland

    Roman Fasel, Manfred Parschau & Karl-Heinz Ernst

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  1. Roman Fasel
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  2. Manfred Parschau
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  3. Karl-Heinz Ernst
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Correspondence to Karl-Heinz Ernst.

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Reprints and permissions information is available at npg.nature.com/reprintsandpermissions. The authors declare no competing financial interests.

Supplementary information

Supplementary Methods

This file describes the experimental procedures and gives detail on the molecular mechanics calculations. (PDF 149 kb)

Supplementary Figure 1

This figure describes the segregation of enantiomeric excess to steps and into residual areas. (PDF 124 kb)

Supplementary Figure 2

This figure describes the calculated energy cost when single M- or P- heptahelicene molecules in λ and ρ domains are substituted by opposite enantiomers. (PDF 205 kb)

Supplementary Figure 3

This figure describes the higher energy content of mirror domain boundaries with respect to rotational domain boundaries. (PDF 453 kb)

Supplementary Figure 4

This figure describes the calculation of the energy at the interface between a l domain edge and excess molecules of different handedness. (PDF 156 kb)

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Fasel, R., Parschau, M. & Ernst, KH. Amplification of chirality in two-dimensional enantiomorphous lattices. Nature 439, 449–452 (2006). https://doi.org/10.1038/nature04419

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