Two-Dimensional Nonbenzenoid Heteroacene Crystals Synthesized via In-Situ Embedding of Ladder Bipyrazinylenes on Au(111)
© 2024 Wiley-VCH GmbH..
Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π-electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two-dimensional (2D) crystals on surfaces is still a great challenge. By in-situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds. Using bond-resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o-diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:63 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 63(2024), 11 vom: 11. März, Seite e202318142 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Wang, Ying [VerfasserIn] |
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| Links: |
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| Themen: |
2D Molecular Crystal |
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| Anmerkungen: |
Date Revised 04.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202318142 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| 520 | |a Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π-electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two-dimensional (2D) crystals on surfaces is still a great challenge. By in-situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds. Using bond-resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o-diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a 2D Molecular Crystal | |
| 650 | 4 | |a Heteroacene | |
| 650 | 4 | |a On-Surface Synthesis | |
| 650 | 4 | |a Scanning Tunneling Microscopy | |
| 650 | 4 | |a Topological Defect | |
| 700 | 1 | |a Gong, Wen-Wen |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 Kang, Li-Xia |e verfasserin |4 aut | |
| 700 | 1 | |a Sha, Feng |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Zheng-Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Jian-Wei |e verfasserin |4 aut | |
| 700 | 1 | |a Han, Yan-Jie |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Peng |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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