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Updated: May 24, 2026

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Structural diversity in coordination self-assembled networks of a multimodal ligand azacalix[4]pyrazine
Jin-Cheng Wu1, Liang Zhao, De-Xian Wang
1The Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Abstract:
We report herein the synthesis of a new heteracalixaromatic compound, tetramethylazacalix[4]pyrazine (TAPz), and its coordination self-assemblies with metal and metal cluster centers. Structural characterization of TAPz has shown that its conformation is fluxional in solution but exhibits a dominant 1,3-alternate configuration in the crystalline solid state, wherein its convergent chelating coordination sites are orthogonal to the 120°-angled bridging sites, thus forming a unique multimodal ligand. Compound TAPz reacting with silver, zinc metal centers, and Cu(x)I(x) cluster centers leads to the construction of diverse coordination network structures in 1-5 including honeycomb, Kagomé, α-quartz, and cavity-involved two-dimensional layers. The structural diversity of these network structures is conducted by different combination modes between the chelation bonding sites of TAPz and metal or metal cluster centers. This system may afford deeper insight on the fantastic use of macrocyclic compounds on the designed synthesis of coordination network structures through the proper arrangement of their coordination sites.
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