Topological Derivative Strategy for Large-Pore Three-Dimensional Covalent Organic Frameworks
The pursuit of three-dimensional covalent organic frameworks (3D COFs) with ultralarge pores faces fundamental challenges from structural interpenetration. We address this limitation through a topology-driven design strategy that transforms edge-transitive <i>scu</i> nets into two distinct derivative frameworks─<i>mmm</i> and <i>jcg</i>─via symmetry-controlled monomer selection. This approach yields contrasting pore evolution behaviors: while <i>mmm</i> series COFs (JUC-693 to JUC-695) show unpredictable pore size fluctuations (2.6 → 3.9 → 1.2 nm) due to complex interpenetration patterns, <i>jcg</i> series frameworks (JUC-696 to JUC-698) exhibit controlled expansion up to a record of 5.1 nm pore diameter in JUC-698. Comprehensive characterization, including macromolecular encapsulation studies with vitamin B12 and myoglobin, confirms the structural integrity and accessibility of these engineered pores. Our findings establish topology-directed design as a powerful tool for overcoming interpenetration barriers in porous materials development.
Authors
- Valentin Valtchev (ORCID: https://orcid.org/0000-0002-2341-6397)
- Fengqian Chen (ORCID: https://orcid.org/0000-0002-2330-6403)
- Qianrong Fang (ORCID: https://orcid.org/0000-0003-3365-5508)
- Haorui Zheng (ORCID: https://orcid.org/0009-0004-5305-9062)
- Y. Wang (ORCID: https://orcid.org/0009-0003-6680-5813)
- Jie Ji (ORCID: https://orcid.org/0000-0001-5805-9978)
- Hui Li (ORCID: https://orcid.org/0000-0002-2689-2241)
- Shilun Qiu
- Dan Zhao (ORCID: https://orcid.org/0000-0002-4427-2150)
- Jinquan Suo
- Jialong Song
Institutions
- Centre National de la Recherche Scientifique (FR)
- National University of Singapore (SG)
- Jilin University (CN)
- Chinese Academy of Sciences (CN)
- Normandie Université (FR)
- Laboratoire Catalyse et Spectrochimie (FR)
- Jilin Medical University (CN)
- Qingdao Institute of Bioenergy and Bioprocess Technology (CN)
- Zhuhai Institute of Advanced Technology (CN)
- State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
- Université de Caen Normandie (FR)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-10-21
- DOI
- https://doi.org/10.1021/jacs.5c10534
- Citations
- 2
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.04
Funders
- National Natural Science Foundation of China
- Overseas Expertise Introduction Center for Discipline Innovation of Food Nutrition and Human Health (111 Center)