Constructing an 8-Connected Hydrogen-Bonded Organic Framework with Hafnium-Oxo Clusters

Hydrogen-bonded organic frameworks (HOFs) exhibit intriguing structural features with potential applications in various fields. However, constructing HOFs based on high-connectivity nodes is a challenging task. In this study, we report the synthesis of three new metal-hydrogen-bonded organic frameworks (M-HOFs), <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4</b><b>/<i>n</i></b>, <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b>, and <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b>, based on a charge-neutral tetranuclear hafnium-oxo cluster [Hf<sub>4</sub>(μ<sub>2</sub>-OH)<sub>8</sub>L<sub>8</sub>] (L = 1H-benzimidazole-2-carboxylate) as the building unit. The rigid benzimidazole-carboxylate ligand maintains the cluster's symmetry while providing hydrogen-bonding sites. By modulating crystallization conditions, three distinct supramolecular packing modes are achieved: <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4</b><b>/<i>n</i></b> forms an <i><b>sql</b></i> net via four pairs of hydrogen bonds and four groups of DMF-mediated van der Waals interactions between [Hf<sub>4</sub>(μ<sub>2</sub>-OH)<sub>8</sub>L<sub>8</sub>] units; <b>Hf</b><sub><b>4</b></sub><b>-<i>Fddd</i>-1</b> adopts a rarely seen 8-connected <i><b>tsi</b></i> net through eight pairs of intercluster hydrogen bonds; <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b> exhibits a <i><b>dia</b></i> net with only four pairs of hydrogen bonds per cluster. Framework stability correlates with interaction strength and number. Notably, <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4/</b><i><b>n</b></i> and <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b> show superior solvent stability compared to <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b>. Porosity analysis reveals that <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b> possesses interconnected channels, with a void fraction of 31.1% and a surface area of 277.7 m<sup>2</sup>/g. This work highlights metal-oxo clusters as potential building units for synthesizing complex HOFs with high-connectivity nodes.

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Journal
Inorganic Chemistry
Published
2025-09-29
DOI
https://doi.org/10.1021/acs.inorgchem.5c03602
Citations
1
Primary Topic
Metal-Organic Frameworks: Synthesis and Applications
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article
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article

Constructing an 8-Connected Hydrogen-Bonded Organic Framework with Hafnium-Oxo Clusters

Jun‐Rui Liu, Wei Wang, Yongjie Zhou, Jie Zhao et al.
1 citations
Inorganic Chemistry
Metal-Organic Frameworks: Synthesis and Applications
0.54
article

Constructing an 8-Connected Hydrogen-Bonded Organic Framework with Hafnium-Oxo Clusters

Jun‐Rui Liu, Wei Wang, Yongjie Zhou, Jie Zhao, Zi‐Ang Nan, Yulong Zhang, Zhu Zhuo, You‐Gui Huang, Zuo-Bei Wang, Linxia Tang
article en
1 citations

Abstract

Hydrogen-bonded organic frameworks (HOFs) exhibit intriguing structural features with potential applications in various fields. However, constructing HOFs based on high-connectivity nodes is a challenging task. In this study, we report the synthesis of three new metal-hydrogen-bonded organic frameworks (M-HOFs), <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4</b><b>/<i>n</i></b>, <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b>, and <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b>, based on a charge-neutral tetranuclear hafnium-oxo cluster [Hf<sub>4</sub>(μ<sub>2</sub>-OH)<sub>8</sub>L<sub>8</sub>] (L = 1H-benzimidazole-2-carboxylate) as the building unit. The rigid benzimidazole-carboxylate ligand maintains the cluster's symmetry while providing hydrogen-bonding sites. By modulating crystallization conditions, three distinct supramolecular packing modes are achieved: <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4</b><b>/<i>n</i></b> forms an <i><b>sql</b></i> net via four pairs of hydrogen bonds and four groups of DMF-mediated van der Waals interactions between [Hf<sub>4</sub>(μ<sub>2</sub>-OH)<sub>8</sub>L<sub>8</sub>] units; <b>Hf</b><sub><b>4</b></sub><b>-<i>Fddd</i>-1</b> adopts a rarely seen 8-connected <i><b>tsi</b></i> net through eight pairs of intercluster hydrogen bonds; <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b> exhibits a <i><b>dia</b></i> net with only four pairs of hydrogen bonds per cluster. Framework stability correlates with interaction strength and number. Notably, <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>P</b></i><b>4/</b><i><b>n</b></i> and <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b> show superior solvent stability compared to <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-2</b>. Porosity analysis reveals that <b>Hf</b><sub><b>4</b></sub><b>-</b><i><b>Fddd</b></i><b>-1</b> possesses interconnected channels, with a void fraction of 31.1% and a surface area of 277.7 m<sup>2</sup>/g. This work highlights metal-oxo clusters as potential building units for synthesizing complex HOFs with high-connectivity nodes.

Inorganic ChemistryVol. 64(40)
Chinese Academy of Sciences (CN), Xiamen Institute of Rare-earth Materials (CN), Fujian Institute of Research on the Structure of Matter (CN), University of Chinese Academy of Sciences (CN), Fuzhou University (CN)
Openalex Percentile: Top 30%
Metal-Organic Frameworks: Synthesis and Applications
0.54
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