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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2024-11-01
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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 |
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| 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. |
| format | Article |
| id | doaj-art-e107346fa09d4f96954936e1c410ac7f |
| institution | DOAJ |
| issn | 2079-4991 |
| language | English |
| publishDate | 2024-11-01 |
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| series | Nanomaterials |
| 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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