From Helical to Planar Chirality by On-surface Chemistry

Overview

Journal Nat Chem

Specialty Chemistry

Date 2017 Feb 22

PMID 28221353

Citations 20

Authors

Oleksandr Stetsovych

Martin Svec

Jaroslav Vacek

Jana Vacek Chocholousova

Andrej Jancarik

Jiri Rybacek

Krzysztof Kosmider

Irena G Stara

Pavel Jelinek

Ivo Stary

Affiliations

Soon will be listed here.

Abstract

The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic-inorganic chiral interfaces.

Citing Articles

Diastereomeric Configuration Drives an On-Surface Specific Rearrangement into Low Bandgap Non-Benzenoid Graphene Nanoribbons.

Villalobos F, Mendieta-Moreno J, Lobo-Checa J, Morcillo S, Martinez J, Gomez-Fernandez J J Am Chem Soc. 2025; 147(9):7245-7254.

PMID: 39971275 PMC: 11887059. DOI: 10.1021/jacs.4c10478.

Direct flipping dynamics and quantized enrichment of chirality at single-molecule resolution.

Hu W, Zhang Z, Xiong W, Li M, Yan Y, Yang C Sci Adv. 2024; 10(28):eado1125.

PMID: 38996014 PMC: 11244442. DOI: 10.1126/sciadv.ado1125.

On-surface cyclization of vinyl groups on poly-para-phenylene involving an unusual pentagon to hexagon transformation.

Giovannantonio M, Qiu Z, Pignedoli C, Asako S, Ruffieux P, Mullen K Nat Commun. 2024; 15(1):1910.

PMID: 38429274 PMC: 10907692. DOI: 10.1038/s41467-024-46173-3.

On-Surface Synthesis of Anthracene-Fused Zigzag Graphene Nanoribbons from 2,7-Dibromo-9,9'-bianthryl Reveals Unexpected Ring Rearrangements.

Xu X, Kinikar A, Giovannantonio M, Pignedoli C, Ruffieux P, Mullen K Precis Chem. 2024; 2(2):81-87.

PMID: 38425747 PMC: 10900509. DOI: 10.1021/prechem.3c00116.

Chirality variation from self-assembly on Ullmann coupling for the DBCh adsorbate on Au(111) and Ag(111).

Wang H, Hu J, Liang Z, Zhang H, Huang C, Xie L Nanoscale Adv. 2023; 5(5):1368-1377.

PMID: 36866267 PMC: 9972870. DOI: 10.1039/d2na00789d.

References

Gourdon A . On-surface covalent coupling in ultrahigh vacuum. Angew Chem Int Ed Engl. 2008; 47(37):6950-3. DOI: 10.1002/anie.200802229. View

Fasel R, Parschau M, Ernst K . Amplification of chirality in two-dimensional enantiomorphous lattices. Nature. 2006; 439(7075):449-52. DOI: 10.1038/nature04419. View

Mendez J, Lopez M, Martin-Gago J . On-surface synthesis of cyclic organic molecules. Chem Soc Rev. 2011; 40(9):4578-90. DOI: 10.1039/c0cs00161a. View

Haq S, Liu N, Humblot V, Jansen A, Raval R . Drastic symmetry breaking in supramolecular organization of enantiomerically unbalanced monolayers at surfaces. Nat Chem. 2011; 1(5):409-14. DOI: 10.1038/nchem.295. View

Sun K, Shao T, Xie J, Lan M, Yuan H, Xiong Z . Chiral pinwheel clusters lacking local point chirality. Small. 2012; 8(13):2078-82. DOI: 10.1002/smll.201200168. View

Parschau M, Fasel R, Ernst K, Groning O, Brandenberger L, Schillinger R . Buckybowls on metal surfaces: symmetry mismatch and enantiomorphism of corannulene on Cu110. Angew Chem Int Ed Engl. 2007; 46(43):8258-61. DOI: 10.1002/anie.200700610. View

Parschau M, Romer S, Ernst K . Induction of homochirality in achiral enantiomorphous monolayers. J Am Chem Soc. 2004; 126(47):15398-9. DOI: 10.1021/ja044136z. View

Zhang X, Zeng Q, Wang C . On-surface single molecule synthesis chemistry: a promising bottom-up approach towards functional surfaces. Nanoscale. 2013; 5(18):8269-87. DOI: 10.1039/c3nr01611k. View

Demers-Carpentier V, Rasmussen A, Goubert G, Ferrighi L, Dong Y, Lemay J . Stereodirection of an α-ketoester at sub-molecular sites on chirally modified Pt(111): heterogeneous asymmetric catalysis. J Am Chem Soc. 2013; 135(27):9999-10002. DOI: 10.1021/ja403955k. View

10.

Kichin G, Weiss C, Wagner C, Tautz F, Temirov R . Single molecule and single atom sensors for atomic resolution imaging of chemically complex surfaces. J Am Chem Soc. 2011; 133(42):16847-51. DOI: 10.1021/ja204624g. View

11.

Pinardi A, Otero-Irurueta G, Palacio I, Martinez J, Sanchez-Sanchez C, Tello M . Tailored formation of N-doped nanoarchitectures by diffusion-controlled on-surface (cyclo)dehydrogenation of heteroaromatics. ACS Nano. 2013; 7(4):3676-84. DOI: 10.1021/nn400690e. View

12.

Pavlicek N, Schuler B, Collazos S, Moll N, Perez D, Guitian E . On-surface generation and imaging of arynes by atomic force microscopy. Nat Chem. 2015; 7(8):623-8. DOI: 10.1038/nchem.2300. View

13.

Gross L, Mohn F, Moll N, Liljeroth P, Meyer G . The chemical structure of a molecule resolved by atomic force microscopy. Science. 2009; 325(5944):1110-4. DOI: 10.1126/science.1176210. View

14.

Pinardi A, Martinez J, Jancarik A, Stara I, Stary I, Lopez M . Sequential formation of N-doped nanohelicenes, nanographenes and nanodomes by surface-assisted chemical (cyclo)dehydrogenation of heteroaromatics. Chem Commun (Camb). 2014; 50(13):1555-7. DOI: 10.1039/c3cc47399f. View

15.

Stohr M, Boz S, Schar M, Nguyen M, Pignedoli C, Passerone D . Self-assembly and two-dimensional spontaneous resolution of cyano-functionalized [7]helicenes on Cu111. Angew Chem Int Ed Engl. 2011; 50(42):9982-6. DOI: 10.1002/anie.201102627. View

16.

Berger R, Fuchter M, Krossing I, Rzepa H, Schaefer J, Scherer H . Gold(I) mediated rearrangement of [7]-helicene to give a benzo[cd]pyrenium cation embedded in a chiral framework. Chem Commun (Camb). 2013; 50(40):5251-3. DOI: 10.1039/c3cc46986g. View

17.

Gross L, Mohn F, Moll N, Schuler B, Criado A, Guitian E . Bond-order discrimination by atomic force microscopy. Science. 2012; 337(6100):1326-9. DOI: 10.1126/science.1225621. View

18.

Wang D, Katz T, Golen J, Rheingold A . Diels-Alder additions of benzynes within helicene skeletons. J Org Chem. 2004; 69(22):7769-71. DOI: 10.1021/jo048707h. View

19.

de Oteyza D, Gorman P, Chen Y, Wickenburg S, Riss A, Mowbray D . Direct imaging of covalent bond structure in single-molecule chemical reactions. Science. 2013; 340(6139):1434-7. DOI: 10.1126/science.1238187. View

20.

Jancarik A, Rybacek J, Cocq K, Chocholousova J, Vacek J, Pohl R . Rapid access to dibenzohelicenes and their functionalized derivatives. Angew Chem Int Ed Engl. 2013; 52(38):9970-5. DOI: 10.1002/anie.201301739. View