Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess
Abstract The investigation of chirality at the nanoscale is important to bridge the gap between molecular and macroscopic chirality. Atomically precise metal nanoclusters provide an ideal platform for this research, while their enantiopure preparation poses a challenge. Here, we describe an efficien...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-06-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-39462-w |
| _version_ | 1827916912140484608 |
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| author | Chang Liu Yan Zhao Tai-Song Zhang Cheng-Bo Tao Wenwen Fei Sheng Zhang Man-Bo Li |
| author_facet | Chang Liu Yan Zhao Tai-Song Zhang Cheng-Bo Tao Wenwen Fei Sheng Zhang Man-Bo Li |
| author_sort | Chang Liu |
| collection | DOAJ |
| description | Abstract The investigation of chirality at the nanoscale is important to bridge the gap between molecular and macroscopic chirality. Atomically precise metal nanoclusters provide an ideal platform for this research, while their enantiopure preparation poses a challenge. Here, we describe an efficient approach to enantiopure metal nanoclusters via asymmetric transformation, that is, achiral Au23(SC6H11)16 nanoclusters are converted into chiral and enantiopure Au24(L)2(SC6H11)16 nanoclusters by a chiral inducer phosphoramidite (L). Two enantiomers of Au24(L)2(SC6H11)16 are obtained and the crystal structures reveal their hierarchical chirality, which originates from the two introduced chiral L molecules, the transformation-triggered asymmetric rearrangement of the staple motifs on the surface of the gold core, and the helical arrangement of nanocluster molecules. The construction of this type of enantiomerically pure nanoclusters is achieved based on the easy-to-synthesize and modular L. Lastly, the chirality-related chiroptical performance was investigated, revealing a negative nonlinear CD-ee dependence. |
| first_indexed | 2024-03-13T03:20:24Z |
| format | Article |
| id | doaj.art-aab6d589dd2f4790b74b4a2c73d93f71 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T03:20:24Z |
| publishDate | 2023-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-aab6d589dd2f4790b74b4a2c73d93f712023-06-25T11:21:28ZengNature PortfolioNature Communications2041-17232023-06-0114111010.1038/s41467-023-39462-wAsymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excessChang Liu0Yan Zhao1Tai-Song Zhang2Cheng-Bo Tao3Wenwen Fei4Sheng Zhang5Man-Bo Li6Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityInstitutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui UniversityAbstract The investigation of chirality at the nanoscale is important to bridge the gap between molecular and macroscopic chirality. Atomically precise metal nanoclusters provide an ideal platform for this research, while their enantiopure preparation poses a challenge. Here, we describe an efficient approach to enantiopure metal nanoclusters via asymmetric transformation, that is, achiral Au23(SC6H11)16 nanoclusters are converted into chiral and enantiopure Au24(L)2(SC6H11)16 nanoclusters by a chiral inducer phosphoramidite (L). Two enantiomers of Au24(L)2(SC6H11)16 are obtained and the crystal structures reveal their hierarchical chirality, which originates from the two introduced chiral L molecules, the transformation-triggered asymmetric rearrangement of the staple motifs on the surface of the gold core, and the helical arrangement of nanocluster molecules. The construction of this type of enantiomerically pure nanoclusters is achieved based on the easy-to-synthesize and modular L. Lastly, the chirality-related chiroptical performance was investigated, revealing a negative nonlinear CD-ee dependence.https://doi.org/10.1038/s41467-023-39462-w |
| spellingShingle | Chang Liu Yan Zhao Tai-Song Zhang Cheng-Bo Tao Wenwen Fei Sheng Zhang Man-Bo Li Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess Nature Communications |
| title | Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| title_full | Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| title_fullStr | Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| title_full_unstemmed | Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| title_short | Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| title_sort | asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess |
| url | https://doi.org/10.1038/s41467-023-39462-w |
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