Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives
Barbituric acid derivative (TDPT) is an achiral molecule, and its adsorption on a surface results in two opposite enantiomerically oriented motifs, namely TDPT-S<sub>p</sub> and R<sub>p</sub>. Two types of building blocks can be formed; block I is enantiomer-pure and is built...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-08-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/16/2304 |
| _version_ | 1797583626988158976 |
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| author | Fabien Silly Changzhi Dong François Maurel Xiaonan Sun |
| author_facet | Fabien Silly Changzhi Dong François Maurel Xiaonan Sun |
| author_sort | Fabien Silly |
| collection | DOAJ |
| description | Barbituric acid derivative (TDPT) is an achiral molecule, and its adsorption on a surface results in two opposite enantiomerically oriented motifs, namely TDPT-S<sub>p</sub> and R<sub>p</sub>. Two types of building blocks can be formed; block I is enantiomer-pure and is built up of the same motifs (format S<sub>p</sub>S<sub>p</sub> or R<sub>p</sub>R<sub>p</sub>) whereas block II is enantiomer-mixed and composes both motifs (format S<sub>p</sub>R<sub>p</sub>), respectively. The organization of the building blocks determines the formation of different nanoarchitectures which are investigated using scanning tunneling microscopy at a liquid/HOPG interface. Sophisticated, highly symmetric “nanowaves” are first formed from both building blocks I and II and are heterochiral. The “nanowaves” are metastable and evolve stepwisely into more close-packed “nanowires” which are formed from enantiomer-pure building block I and are homochiral. A dynamic hetero- to homochiral transformation and simultaneous multi-scale phase transitions are demonstrated at the single-molecule level. Our work provides novel insights into the control and the origin of chiral assemblies and chiral transitions, revealing the various roles of enantiomeric selection and chiral competition, driving forces, stability and molecular coverage. |
| first_indexed | 2024-03-10T23:41:29Z |
| format | Article |
| id | doaj.art-6deae933144f4ffba28dfcb46f1fa67e |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-10T23:41:29Z |
| publishDate | 2023-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-6deae933144f4ffba28dfcb46f1fa67e2023-11-19T02:27:01ZengMDPI AGNanomaterials2079-49912023-08-011316230410.3390/nano13162304Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid DerivativesFabien Silly0Changzhi Dong1François Maurel2Xiaonan Sun3TITANS, SPEC, CEA, CNRS, Université Paris-Saclay, 91191 Gif sur Yvette, FranceITODYS, CNRS UMR 7086, Université Paris Cité, 15 rue Jean Antoine de Baïf, 75013 Paris, FranceITODYS, CNRS UMR 7086, Université Paris Cité, 15 rue Jean Antoine de Baïf, 75013 Paris, FranceITODYS, CNRS UMR 7086, Université Paris Cité, 15 rue Jean Antoine de Baïf, 75013 Paris, FranceBarbituric acid derivative (TDPT) is an achiral molecule, and its adsorption on a surface results in two opposite enantiomerically oriented motifs, namely TDPT-S<sub>p</sub> and R<sub>p</sub>. Two types of building blocks can be formed; block I is enantiomer-pure and is built up of the same motifs (format S<sub>p</sub>S<sub>p</sub> or R<sub>p</sub>R<sub>p</sub>) whereas block II is enantiomer-mixed and composes both motifs (format S<sub>p</sub>R<sub>p</sub>), respectively. The organization of the building blocks determines the formation of different nanoarchitectures which are investigated using scanning tunneling microscopy at a liquid/HOPG interface. Sophisticated, highly symmetric “nanowaves” are first formed from both building blocks I and II and are heterochiral. The “nanowaves” are metastable and evolve stepwisely into more close-packed “nanowires” which are formed from enantiomer-pure building block I and are homochiral. A dynamic hetero- to homochiral transformation and simultaneous multi-scale phase transitions are demonstrated at the single-molecule level. Our work provides novel insights into the control and the origin of chiral assemblies and chiral transitions, revealing the various roles of enantiomeric selection and chiral competition, driving forces, stability and molecular coverage.https://www.mdpi.com/2079-4991/13/16/23042D chiralheterochiralhomochiralenantiomerself-assemblyhydrogen bond |
| spellingShingle | Fabien Silly Changzhi Dong François Maurel Xiaonan Sun Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives Nanomaterials 2D chiral heterochiral homochiral enantiomer self-assembly hydrogen bond |
| title | Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives |
| title_full | Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives |
| title_fullStr | Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives |
| title_full_unstemmed | Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives |
| title_short | Two-Dimensional Hetero- to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives |
| title_sort | two dimensional hetero to homochiral phase transition from dynamic adsorption of barbituric acid derivatives |
| topic | 2D chiral heterochiral homochiral enantiomer self-assembly hydrogen bond |
| url | https://www.mdpi.com/2079-4991/13/16/2304 |
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