A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation.

Autor: Chen W; Southern University of Science and Technology, Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, 518055, Shenzhen, CHINA., Xu N; Southern University of Science and Technology, Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, 518055, Shenzhen, CHINA., Qin L; Southern University of Science and Technology, Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, 518055, Shenzhen, CHINA., Deng YF; Southern University of Science and Technology, Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, 518055, Shenzhen, CHINA., Zhuang GL; Zhejiang University of Technology, College of Chemical Engineering, 310032, Hangzhou, CHINA., Zhang Z; Guangzhou University, Institute of Environmental Research at Greater Bay Area, 510006, Guangzhou, CHINA., Xie TZ; Guangzhou University, Institute of Environmental Research at Greater Bay Area, 510006, Guangzhou, CHINA., Wang P; Guangzhou University, Institute of Environmental Research at Greater Bay Area, 510006, Guangzhou, CHINA., Zheng Z; Southern University of Science and Technology, Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, ., 518055, Shenzhen, CHINA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Nov 12, pp. e202420770. Date of Electronic Publication: 2024 Nov 12.
DOI: 10.1002/anie.202420770
Abstrakt: Lanthanide-containing clusters are synthetically Lanthanide-containing clusters are synthetically challenging and with significant chemical and materials applications. Herein, two isostructural heterometallic clusters of the formula (NO3)12@[Ln132Ni78(OH)292(IDA)48(CH3COO)96(NO3)12(H2O)78]Cl44·xH2O·yCH3OH (IDA = iminodiacetate; Ln = Gd 1, x = 110, y = 0; Ln = Eu 2, x = 95, y = 40) were obtained via co-hydrolysis of Ln3+ (Gd3+ or Eu3+) and Ni2+ in the presence of iminodiacetate (IDA). Crystallographic studies show that each features a truncated tetrahedral core of Ln132Ni78 within which a void of 5.5 Å in diameter; connecting the central cage and its exterior are four trumpet-like passageways surface-decorated with dinuclear units of [Gd(μ3-OH)2Gd]. Mass spectroscopic analyses indicate that both clusters maintained their structural integrity in aqueous solution, with cryo-electron microscopy providing the most convincing visual evidence in support of the cluster's solution stability. Size-selective Knoevenagel condensation, believed to occur in the passageways on the basis of experimental and molecular modeling results, was achieved in the presence of 1. The application of 1 as a uniquely structured molecular reactor and a recyclable heterogeneous catalyst was further illustrated by the one-pot three-component synthesis of biologically and pharmaceutically significant 4H-pyran derivatives.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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