Construction of zirconium/hafnium-oxo clusters based on a new protection-calix[8]arene

Fei-Fei Wang; Baoshan Hou

doi:10.1039/d4dt00169a

Construction of zirconium/hafnium-oxo clusters based on a new protection-calix[8]arene

Dalton Trans. 2024 Apr 16;53(15):6507-6514. doi: 10.1039/d4dt00169a.

Authors

Fei-Fei Wang¹, Baoshan Hou²

Affiliations

¹ Department of Chemistry, Xinzhou Normal University, Xinzhou, 034000, China. wangff718@nenu.edu.cn.
² Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, and Westlake Institute for Advanced Study, 600 Dunyu Road, Zhejiang, Hangzhou, 310030, China. houbaoshan@westlake.edu.cn.

PMID: 38512102
DOI: 10.1039/d4dt00169a

Abstract

Calix[8]arene has been used as a promising type of macrocyclic ligand for the construction of multinuclear metal-oxo clusters (MOCs), but not for zirconium/hafnium-oxo clusters (Zr/HfOCs). In this paper, we report the first series of ZrOCs (HfOCs) based on calix[8]arene: Zr4, Zr8, Hf4, and Hf8. Zr8/Hf8 has a rhombohedral conformation and can be regarded as a derivative of the octahedral Zr₆ cluster. Remarkably, I₂ adsorption experiments indicate that Zr4 (Zr8) adsorbs much faster than Hf4 (Hf8). Density functional theory (DFT) calculations show that metallic Zr atoms interact more strongly with I₂ than metallic Hf atoms. The successful application of calix[8]arene for the synthesis of well-defined ZrOCs (HfOCs) shows a bright future for MOCs protected by macrocyclic ligands.