You are here

From helical to planar chirality by on-surface chemistry

Oleksandr Stetsovych1, Martin Švec1, Krzysztof Kosmider1, Pavel Jelínek1, Jaroslav Vacek2, Jana Vacek Chocholoušová2, Andrej Jančařík2, Jiří Rybáček2, Irena G. Stará2, Ivo Starý2

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.

Transformation of chiral molecules on the surface of the solid allows the same chirality of the adsorbed molecules to be achieved throughout the monolayer. This arrangement is impossible to achieve by simply depositing prochiral molecules on the solid surface (see processes labeled B and C).

1Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21 Prague 8, Czech Republic
2Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic