Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111)
On-surface chemistry provides an efficient approach to construction of diverse covalent architectures with atomic precision, ranging from one-dimensional chains and ribbons to two-dimensional covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) on coinage metal substrates. This stu...
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| Language: | English |
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Elsevier
2025-04-01
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| Series: | Carbon Trends |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667056925000240 |
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| author | Yifan Liang Jianing Wang Ruoting Yin Zhengya Wang Xiaoqing Wang Jie Meng Shijing Tan Chuanxu Ma Qunxiang Li Bing Wang |
| author_facet | Yifan Liang Jianing Wang Ruoting Yin Zhengya Wang Xiaoqing Wang Jie Meng Shijing Tan Chuanxu Ma Qunxiang Li Bing Wang |
| author_sort | Yifan Liang |
| collection | DOAJ |
| description | On-surface chemistry provides an efficient approach to construction of diverse covalent architectures with atomic precision, ranging from one-dimensional chains and ribbons to two-dimensional covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) on coinage metal substrates. This study explores a distinct on-surface pyrolysis approach to MOFs derived from a crown ether molecular precursor on Au(111) and Ag(111) surfaces. Utilizing scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) combined with density functional theory (DFT) calculations, we elucidate the adsorption behavior and the characteristic macrocyclic configuration of the crown ether on Au(111). Subsequent surface-catalyzed Ullmann coupling reactions at an annealing temperature of 470 K lead to highly disordered COFs with the formation of four-membered and six-membered rings through dimerization and trimerization. For the Ag(111) surface, further annealing at 520 K initiates a unique dehydrogenative reaction within the macrocyclic rings, resulting in the loss of six hydrogen atoms. At an elevated temperature of 720 K, breaking of the second C−O bonds yields a long-range ordered triphenylene-based MOF structure. Electronic characterizations reveal the presence of both regular and diatomic kagome lattices, together with distinct quantum-dot states emerging in the pore regions. Additionally, we investigate the selective encapsulation of single guest picenes within the MOF structure, emphasizing the potential of triphenylene-based frameworks for advanced applications in sensing and molecular filtering. Our findings provide a comprehensive insight into the chemical reactivity of crown ethers on metal substrates and demonstrate a novel pathway to designing MOFs through an on-surface pyrolysis process. |
| format | Article |
| id | doaj-art-bf1bd5796a3e41a4b6316736a1b189af |
| institution | Kabale University |
| issn | 2667-0569 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Carbon Trends |
| spelling | doaj-art-bf1bd5796a3e41a4b6316736a1b189af2025-01-31T05:12:38ZengElsevierCarbon Trends2667-05692025-04-0119100474Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111)Yifan Liang0Jianing Wang1Ruoting Yin2Zhengya Wang3Xiaoqing Wang4Jie Meng5Shijing Tan6Chuanxu Ma7Qunxiang Li8Bing Wang9Hefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR China; Corresponding authors.Hefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR ChinaHefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information & Quantum Physics, New Cornerstone Science Laboratory, University of Science and Technology of China, Hefei 230026, PR China; Hefei National Laboratory, University of Science and Technology of China, Hefei 230088, PR China; Corresponding authors.On-surface chemistry provides an efficient approach to construction of diverse covalent architectures with atomic precision, ranging from one-dimensional chains and ribbons to two-dimensional covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) on coinage metal substrates. This study explores a distinct on-surface pyrolysis approach to MOFs derived from a crown ether molecular precursor on Au(111) and Ag(111) surfaces. Utilizing scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) combined with density functional theory (DFT) calculations, we elucidate the adsorption behavior and the characteristic macrocyclic configuration of the crown ether on Au(111). Subsequent surface-catalyzed Ullmann coupling reactions at an annealing temperature of 470 K lead to highly disordered COFs with the formation of four-membered and six-membered rings through dimerization and trimerization. For the Ag(111) surface, further annealing at 520 K initiates a unique dehydrogenative reaction within the macrocyclic rings, resulting in the loss of six hydrogen atoms. At an elevated temperature of 720 K, breaking of the second C−O bonds yields a long-range ordered triphenylene-based MOF structure. Electronic characterizations reveal the presence of both regular and diatomic kagome lattices, together with distinct quantum-dot states emerging in the pore regions. Additionally, we investigate the selective encapsulation of single guest picenes within the MOF structure, emphasizing the potential of triphenylene-based frameworks for advanced applications in sensing and molecular filtering. Our findings provide a comprehensive insight into the chemical reactivity of crown ethers on metal substrates and demonstrate a novel pathway to designing MOFs through an on-surface pyrolysis process.http://www.sciencedirect.com/science/article/pii/S2667056925000240Metal-organic frameworksCrown etherOn-surface chemistryPyrolysisScanning probe microscopy |
| spellingShingle | Yifan Liang Jianing Wang Ruoting Yin Zhengya Wang Xiaoqing Wang Jie Meng Shijing Tan Chuanxu Ma Qunxiang Li Bing Wang Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) Carbon Trends Metal-organic frameworks Crown ether On-surface chemistry Pyrolysis Scanning probe microscopy |
| title | Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) |
| title_full | Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) |
| title_fullStr | Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) |
| title_full_unstemmed | Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) |
| title_short | Pyrolysis conversion of crown-ether-based covalent networks to kagome metal-organic frameworks on Au(111) and Ag(111) |
| title_sort | pyrolysis conversion of crown ether based covalent networks to kagome metal organic frameworks on au 111 and ag 111 |
| topic | Metal-organic frameworks Crown ether On-surface chemistry Pyrolysis Scanning probe microscopy |
| url | http://www.sciencedirect.com/science/article/pii/S2667056925000240 |
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