Two-Dimensional Crystal Transition from Radialene to Cumulene on Ag(111) via Retro-[2 + 1] Cycloaddition
Two-dimensional (2D) crystal-to-crystal transition is an important method in crystal engineering because of its ability to directly create diverse crystal materials from one crystal. However, steering a 2D single-layer crystal-to-crystal transition on surfaces with high chemo- and stereoselectivity under ultra-high vacuum conditions is a great challenge because the transition is a complex dynamic process. Here, we report a highly chemoselective 2D crystal transition from radialene to cumulene with retention of stereoselectivity on Ag(111) via retro-[2 + 1] cycloaddition of three-membered carbon rings and directly visualize the transition process involving a stepwise epitaxial growth mechanism by the combination of scanning tunneling microscopy and non-contact atomic force microscopy. Using progression annealing, we found that isocyanides on Ag(111) at a low annealing temperature underwent sequential [1 + 1 + 1] cycloaddition and enantioselective molecular recognition based on C-H···Cl hydrogen bonding interactions to form 2D triaza[3]radialene crystals. In contrast, a higher annealing temperature induced the transformation of triaza[3]radialenes to generate trans-diaza[3]cumulenes, which were further assembled into 2D cumulene-based crystals through twofold N-Ag-N coordination and C-H···Cl hydrogen bonding interactions. By combining the observed distinct transient intermediates and density functional theory calculations, we demonstrate that the retro-[2 + 1] cycloaddition reaction proceeds via the ring opening of a three-membered carbon ring, sequential dechlorination/hydrogen passivation, and deisocyanation. Our findings provide new insights into the growth mechanism and dynamics of 2D crystals and have implications for controllable crystal engineering.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:145 |
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| Enthalten in: |
Journal of the American Chemical Society - 145(2023), 24 vom: 21. Juni, Seite 13048-13058 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Liu, Jian-Wei [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 21.06.2023 Date Revised 21.06.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.3c00962 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM357917960 |
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| 245 | 1 | 0 | |a Two-Dimensional Crystal Transition from Radialene to Cumulene on Ag(111) via Retro-[2 + 1] Cycloaddition |
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| 500 | |a Date Revised 21.06.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Two-dimensional (2D) crystal-to-crystal transition is an important method in crystal engineering because of its ability to directly create diverse crystal materials from one crystal. However, steering a 2D single-layer crystal-to-crystal transition on surfaces with high chemo- and stereoselectivity under ultra-high vacuum conditions is a great challenge because the transition is a complex dynamic process. Here, we report a highly chemoselective 2D crystal transition from radialene to cumulene with retention of stereoselectivity on Ag(111) via retro-[2 + 1] cycloaddition of three-membered carbon rings and directly visualize the transition process involving a stepwise epitaxial growth mechanism by the combination of scanning tunneling microscopy and non-contact atomic force microscopy. Using progression annealing, we found that isocyanides on Ag(111) at a low annealing temperature underwent sequential [1 + 1 + 1] cycloaddition and enantioselective molecular recognition based on C-H···Cl hydrogen bonding interactions to form 2D triaza[3]radialene crystals. In contrast, a higher annealing temperature induced the transformation of triaza[3]radialenes to generate trans-diaza[3]cumulenes, which were further assembled into 2D cumulene-based crystals through twofold N-Ag-N coordination and C-H···Cl hydrogen bonding interactions. By combining the observed distinct transient intermediates and density functional theory calculations, we demonstrate that the retro-[2 + 1] cycloaddition reaction proceeds via the ring opening of a three-membered carbon ring, sequential dechlorination/hydrogen passivation, and deisocyanation. Our findings provide new insights into the growth mechanism and dynamics of 2D crystals and have implications for controllable crystal engineering | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Wang, Ying |e verfasserin |4 aut | |
| 700 | 1 | |a Kang, Li-Xia |e verfasserin |4 aut | |
| 700 | 1 | |a Zhao, Yan |e verfasserin |4 aut | |
| 700 | 1 | |a Xing, Guang-Yan |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Zheng-Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Ya-Cheng |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Deng-Yuan |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Pei-Nian |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/jacs.3c00962 |3 Volltext |
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