Constructing an 8-Connected Hydrogen-Bonded Organic Framework with Hafnium-Oxo Clusters
Jie Zhao1,2,3,4, Yu-Long Zhang1,2,3,4, Jun-Rui Liu2,3
1College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China.
Inorganic Chemistry
|September 29, 2025
Summary
Researchers synthesized three new metal-hydrogen-bonded organic frameworks (M-HOFs) using hafnium-oxo clusters. These M-HOFs exhibit diverse structures and varying stability, with one showing promising porosity for applications.
Area of Science:
- Materials Science
- Supramolecular Chemistry
- Coordination Chemistry
Background:
- Hydrogen-bonded organic frameworks (HOFs) offer unique structural properties for diverse applications.
- Synthesizing HOFs with high-connectivity nodes remains a significant challenge in materials chemistry.
Purpose of the Study:
- To report the synthesis of novel metal-hydrogen-bonded organic frameworks (M-HOFs) utilizing a tetranuclear hafnium-oxo cluster.
- To explore different supramolecular packing modes and their impact on framework properties.
- To investigate the stability and porosity of the synthesized M-HOFs.
Main Methods:
- Synthesis of three M-HOFs: Hf4-P4/n, Hf4-Fddd-1, and Hf4-Fddd-2, using a [Hf4(μ2-OH)8L8] cluster (L = 1H-benzimidazole-2-carboxylate).
- Modulation of crystallization conditions to achieve distinct supramolecular packing modes (sql, tsi, dia nets).
- Characterization of framework stability, solvent resistance, porosity, void fraction, and surface area.
Main Results:
- Three distinct M-HOFs were successfully synthesized, featuring varied network topologies (sql, tsi, dia).
- Framework stability was found to correlate with interaction strength and number, with Hf4-P4/n and Hf4-Fddd-1 showing superior solvent stability.
- Hf4-Fddd-1 exhibited interconnected channels with a void fraction of 31.1% and a surface area of 277.7 m²/g.
Conclusions:
- Metal-oxo clusters can serve as effective building units for constructing complex HOFs with high-connectivity nodes.
- Crystallization control allows for the design of M-HOFs with diverse structures and tailored properties.
- The synthesized M-HOFs demonstrate potential for applications requiring porous materials with good stability.
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