Citation: Lihua Liu, Yufeng Liu, Luqing Zhang, Miao Zhang, Pengtao Ma, Guoping Yang. A heptanuclear zirconium cluster-threaded polyoxotungstate wheel for the catalytic synthesis of benzodiazepines[J]. Chinese Chemical Letters, ;2026, 37(12): 111882. doi: 10.1016/j.cclet.2025.111882 shu

A heptanuclear zirconium cluster-threaded polyoxotungstate wheel for the catalytic synthesis of benzodiazepines

Lihua Liu ^{a, 1} ,
Yufeng Liu ^{b, 1} ,
Luqing Zhang ^a ,
Miao Zhang ^a ,
Pengtao Ma ^{a, *,} ,
Guoping Yang ^{b, *,}

a.
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, China
b.
School of Chemistry and Materials Science, Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang 330013, China

mpt@henu.edu.cn

erick@ecut.edu.cn

Received Date: 11 June 2025
Revised Date: 17 September 2025
Accepted Date: 23 September 2025
Available Online: 24 September 2025

Figures(4)

The synthesis of zirconium-based polyoxometalates (POMs) has always been an attractive yet challenging research objective, especially for POMs with high nuclear zirconium cluster. Herein, by introduction of pyrazine-2,3-dicarboxylic acid into the reaction system of K₁₂[H₂P₂W₁₂O₄₈]·24H₂O and ZrOCl₂·8H₂O, a novel threaded phosphotungstate wheel anchored by a heptanuclear zirconium cluster [N(CH₃)₄]₁₈K₂[(Zr₇(OH)₄(PO₄)₂(Pzdc)₄(H₂O)₁₆)(P₆W₃₉O₁₄₇(H₂O)₃)]·43H₂O (H₂Pzdc = pyrazine-2,3-dicarboxylic acid) (Zr₇) has been successfully synthesized via one-pot method and characterized by PXRD pattern, IR spectra and TGA. The analysis of X-ray crystallography reveals that compound Zr₇ crystallizes in the orthorhombic space group Pnma. Notably, compound Zr₇ is currently the largest odd-nuclearity pure zirconium cluster based on POMs. Furthermore, compound Zr₇ exhibits remarkable catalytic activity as a Lewis acid-base catalyst for the cyclization reaction of benzenediamines and 1,3-diketones, affording the valuable 3H-benzo[b][1,4]diazepines up to 99% yield.
- Zr-cluster,
- Polyoxotungstate wheel,
- Polyoxometalates,
- Lewis acid-base catalysis,
- Benzodiazepines
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