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Linker-Flexibility-Induced Triangular Antiprism Nodes in a Three-Dimensional Covalent Organic Framework
Na Yang1, Jiangshan Li1, Lin Li1,2
1College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Flexible linkers enable the creation of novel 3D covalent organic frameworks (COFs) with polyhedral nodes. This study introduces a new 3D COF with high interpenetration and adaptable structure.
Area of Science:
- Materials Science
- Chemistry
- Nanotechnology
Background:
- Rational design of polyhedral nodes is essential for 3D covalent organic frameworks (COFs).
- Polyhedral nodes for 3D COF construction are currently scarce.
- Existing methods often favor 2D connectivity.
Purpose of the Study:
- To demonstrate how linker flexibility can induce polyhedral node geometries.
- To enable the construction of 3D COFs using building blocks favoring 2D connectivity.
- To expand the structural diversity of 3D COFs.
Main Methods:
- Reacting a six-connected building block with a flexible precursor containing C-O single bonds.
- Synthesizing a new highly crystalline 3D COF (3D-TAPB-COF).
- Utilizing continuous rotation electron diffraction analysis up to 1.0 Å resolution.
Main Results:
- The six-connected nodes adopt a triangular antiprism geometry.
- The synthesized 3D-TAPB-COF exhibits an 18-fold interpenetrated pcu topology.
- This represents the highest reported degree of interpenetration in COFs.
- Flexible C-O bonds provide structural adaptability and reversible swelling.
Conclusions:
- Linker flexibility during assembly can induce desired polyhedral node geometries.
- This strategy expands the structural diversity of 3D COFs.
- Provides insights into designing dynamic frameworks with tunable properties.
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