Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates

Semiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chir...

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Main Authors: Maria Yu. Skrypnik, Daria A. Kurtina, Sofia P. Karamysheva, Evgeniia A. Stepanidenko, Irina S. Vasil’eva, Shuai Chang, Alexander I. Lebedev, Roman B. Vasiliev
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Language:English
Published: MDPI AG 2024-11-01
Series:Nanomaterials
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Online Access:https://www.mdpi.com/2079-4991/14/23/1921
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author Maria Yu. Skrypnik
Daria A. Kurtina
Sofia P. Karamysheva
Evgeniia A. Stepanidenko
Irina S. Vasil’eva
Shuai Chang
Alexander I. Lebedev
Roman B. Vasiliev
author_facet Maria Yu. Skrypnik
Daria A. Kurtina
Sofia P. Karamysheva
Evgeniia A. Stepanidenko
Irina S. Vasil’eva
Shuai Chang
Alexander I. Lebedev
Roman B. Vasiliev
author_sort Maria Yu. Skrypnik
collection DOAJ
description Semiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chiral amino and hydroxy acids, which typically contain only one stereocenter. Here, we show the pronounced induction of chirality in atomically thin CdSe nanoplatelets (NPLs) by capping them with enantiopure menthol derivatives as multi-stereocenter molecules. L-(−)/D-(+)-menthyl thioglycolate, easily synthesized from L-(−)/D-(+)-menthol, is attached to Cd-rich (001) basal planes of 2- and 3-monolayer (ML) CdSe NPLs. We show the appearance of narrow sign-alternating bands in the circular dichroism (CD) spectra of 2 ML NPLs corresponding to heavy-hole (HH) and light-hole (LH) excitons with maximal dissymmetry g-factor up to 2.5 × 10<sup>−4</sup>. The most intense CD bands correspond to the lower-energy HH exciton, and in comparison with the N-acetyl-L-Cysteine ligand, the CD bands for L-(−)-menthyl thioglycolate have the opposite sign. The CD measurements are complemented with magnetic CD measurements and first-principles modeling. The obtained results may be of interest for designing new chiral semiconductor nanostructures and improving understanding of their chiroptical properties.
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spelling doaj-art-e107346fa09d4f96954936e1c410ac7f2025-08-20T02:50:34ZengMDPI AGNanomaterials2079-49912024-11-011423192110.3390/nano14231921Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl ThioglycolatesMaria Yu. Skrypnik0Daria A. Kurtina1Sofia P. Karamysheva2Evgeniia A. Stepanidenko3Irina S. Vasil’eva4Shuai Chang5Alexander I. Lebedev6Roman B. Vasiliev7Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaPhysNano Department, ITMO University, Kronverksky pr.49, 197101 St. Petersburg, RussiaPhysNano Department, ITMO University, Kronverksky pr.49, 197101 St. Petersburg, RussiaA. N. Bach Institute of Biochemistry, Research Center of Biotechnology of the Russian Academy of Sciences, Leninsky Ave. 33, Bld. 2, 119071 Moscow, RussiaFaculty of Materials Science, Shenzhen MSU-BIT University, Shenzhen 518115, ChinaDepartment of Physics, Lomonosov Moscow State University, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaSemiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chiral amino and hydroxy acids, which typically contain only one stereocenter. Here, we show the pronounced induction of chirality in atomically thin CdSe nanoplatelets (NPLs) by capping them with enantiopure menthol derivatives as multi-stereocenter molecules. L-(−)/D-(+)-menthyl thioglycolate, easily synthesized from L-(−)/D-(+)-menthol, is attached to Cd-rich (001) basal planes of 2- and 3-monolayer (ML) CdSe NPLs. We show the appearance of narrow sign-alternating bands in the circular dichroism (CD) spectra of 2 ML NPLs corresponding to heavy-hole (HH) and light-hole (LH) excitons with maximal dissymmetry g-factor up to 2.5 × 10<sup>−4</sup>. The most intense CD bands correspond to the lower-energy HH exciton, and in comparison with the N-acetyl-L-Cysteine ligand, the CD bands for L-(−)-menthyl thioglycolate have the opposite sign. The CD measurements are complemented with magnetic CD measurements and first-principles modeling. The obtained results may be of interest for designing new chiral semiconductor nanostructures and improving understanding of their chiroptical properties.https://www.mdpi.com/2079-4991/14/23/19212D semiconductorschiralityCdSe nanoplateletscircular dichroismmentholexcitons
spellingShingle Maria Yu. Skrypnik
Daria A. Kurtina
Sofia P. Karamysheva
Evgeniia A. Stepanidenko
Irina S. Vasil’eva
Shuai Chang
Alexander I. Lebedev
Roman B. Vasiliev
Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
Nanomaterials
2D semiconductors
chirality
CdSe nanoplatelets
circular dichroism
menthol
excitons
title Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
title_full Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
title_fullStr Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
title_full_unstemmed Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
title_short Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
title_sort menthol induced chirality in semiconductor nanostructures chiroptical properties of atomically thin 2d cdse nanoplatelets capped with enantiomeric l d menthyl thioglycolates
topic 2D semiconductors
chirality
CdSe nanoplatelets
circular dichroism
menthol
excitons
url https://www.mdpi.com/2079-4991/14/23/1921
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