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薄荷醇诱导的半导体纳米结构中的手性:用对映体L-(-)/D-(+)-硫代乙醇酸薄荷酯封端的原子级薄二维CdSe纳米片的手性光学性质。

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

作者信息

Skrypnik Maria Yu, Kurtina Daria A, Karamysheva Sofia P, Stepanidenko Evgeniia A, Vasil'eva Irina S, Chang Shuai, Lebedev Alexander I, Vasiliev Roman B

机构信息

Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.

PhysNano Department, ITMO University, Kronverksky pr.49, 197101 St. Petersburg, Russia.

出版信息

Nanomaterials (Basel). 2024 Nov 28;14(23):1921. doi: 10.3390/nano14231921.

DOI:10.3390/nano14231921
PMID:39683309
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11643598/
Abstract

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. 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.

摘要

用手性有机分子包覆的半导体胶体纳米结构是一个研究热点,因为它们在光子学和自旋电子学应用中具有广泛的重要意义。然而,迄今为止,对手性配体的研究几乎完全局限于天然存在的手性氨基酸和羟基酸,这些分子通常只含有一个立体中心。在此,我们展示了通过用对映体纯的薄荷醇衍生物作为多立体中心分子包覆原子级薄的CdSe纳米片(NPLs),可显著诱导其手性。由L-(-)/D-(+)-薄荷醇容易合成的L-(-)/D-(+)-巯基乙酸薄荷酯,附着在2层和3层(ML)CdSe NPLs富含镉的(001)基面上。我们在2 ML NPLs 的圆二色性(CD)光谱中观察到窄的符号交替带的出现,这些带对应于重空穴(HH)和轻空穴(LH)激子,最大不对称g因子高达2.5×10。最强的CD带对应于能量较低的HH激子,与N-乙酰-L-半胱氨酸配体相比,L-(-)-巯基乙酸薄荷酯的CD带具有相反的符号。CD测量辅以磁CD测量和第一性原理建模。所得结果对于设计新型手性半导体纳米结构以及增进对其手性光学性质的理解可能具有重要意义。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/697e7d935c46/nanomaterials-14-01921-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/17408f2c1188/nanomaterials-14-01921-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/97161fb2e529/nanomaterials-14-01921-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/1dd43154e4fe/nanomaterials-14-01921-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/67637f17a198/nanomaterials-14-01921-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/7e514ba8f7fb/nanomaterials-14-01921-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/697e7d935c46/nanomaterials-14-01921-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/17408f2c1188/nanomaterials-14-01921-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/97161fb2e529/nanomaterials-14-01921-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/1dd43154e4fe/nanomaterials-14-01921-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/67637f17a198/nanomaterials-14-01921-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/7e514ba8f7fb/nanomaterials-14-01921-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f473/11643598/697e7d935c46/nanomaterials-14-01921-g006.jpg

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本文引用的文献

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Emerging chiral two-dimensional materials.新兴的手性二维材料。
Nat Chem. 2024 Sep;16(9):1398-1407. doi: 10.1038/s41557-024-01595-w. Epub 2024 Aug 21.
2
Chiroptical Properties of Semiconducting Nanoplatelets Functionalized by Tartrate Derivatives.酒石酸盐衍生物功能化的半导体纳米片的手性光学性质。
Langmuir. 2024 Jun 4;40(22):11481-11490. doi: 10.1021/acs.langmuir.4c00528. Epub 2024 Apr 25.
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Creating chirality in the nearly two dimensions.在近二维空间中创造手性。
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Chiral Induced Spin Selectivity.手性诱导自旋选择性
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Chirality in Atomically Thin CdSe Nanoplatelets Capped with Thiol-Free Amino Acid Ligands: Circular Dichroism vs. Carboxylate Group Coordination.无硫醇氨基酸配体包覆的原子级薄CdSe纳米片的手性:圆二色性与羧酸根基团配位
Materials (Basel). 2024 Jan 1;17(1):237. doi: 10.3390/ma17010237.
6
Induction of Chirality in Atomically Thin ZnSe and CdSe Nanoplatelets: Strengthening of Circular Dichroism via Different Coordination of Cysteine-Based Ligands on an Ultimate Thin Semiconductor Core.原子级薄的ZnSe和CdSe纳米片层中手性的诱导:通过基于半胱氨酸的配体在超薄半导体核上的不同配位增强圆二色性
Materials (Basel). 2023 Jan 26;16(3):1073. doi: 10.3390/ma16031073.
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Liquid crystal-templated chiral nanomaterials: from chiral plasmonics to circularly polarized luminescence.液晶模板化手性纳米材料:从手性等离子体激元到圆偏振发光
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Nanophotonic Approaches for Chirality Sensing.用于手性传感的纳米光子学方法。
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