Enantioselective photoinduced cyclodimerization of a prochiral anthracene derivative adsorbed on helical metal nanostructures
The generation of molecular chirality in the absence of any molecular chiral inductor is challenging and of fundamental interest for developing a better understanding of homochirality. Here, we show the manipulation of molecular chirality through control of the handedness of helical metal nanostruct...
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Published in | Nature chemistry Vol. 12; no. 6; pp. 551 - 559 |
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Main Authors | , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
London
Nature Publishing Group UK
01.06.2020
Nature Publishing Group |
Subjects | |
Online Access | Get full text |
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Summary: | The generation of molecular chirality in the absence of any molecular chiral inductor is challenging and of fundamental interest for developing a better understanding of homochirality. Here, we show the manipulation of molecular chirality through control of the handedness of helical metal nanostructures (referred to as nanohelices) that are produced by glancing angle deposition onto a substrate that rotates in either a clockwise or counterclockwise direction. A prochiral molecule, 2-anthracenecarboxylic acid, is stereoselectively adsorbed on the metal nanohelices as enantiomorphous
anti
-head-to-head dimers. The dimers show either
Si–Si
or
Re–Re
facial stacking depending on the handedness of the nanohelices, which results in a specific enantiopreference during their photoinduced cyclodimerization: a left-handed nanohelix leads to the formation of (+)-cyclodimers, whereas a right-handed one gives (
–
)-cyclodimers. Density functional theory calculations, in good agreement with the experimental results, point to the enantioselectivity mainly arising from the selective spatial matching of either
Si
–
Si
or
Re
–
Re
facial stacking at the helical surface; it may also be influenced by chiroplasmonic effects.
The photoinduced dimerization of a prochiral anthracenecarboxylic acid occurs in an enantioselective fashion when the molecules are adsorbed on helical metal nanostructures. This enantiopreference arises mostly from the helicity of the silver and copper substrates—prepared using shear forces during the deposition process—and may also be influenced by chiroplasmonic effects. |
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ISSN: | 1755-4330 1755-4349 |
DOI: | 10.1038/s41557-020-0453-0 |