A 3D MOF based on Adamantoid Tetracopper(II) and Aminophosphine Oxide Cages: Structural Features and Magnetic and Catalytic Properties
| Autor: | Alexander M. Kirillov, Ewelina I. Śliwa, Dmytro S. Nesterov, Julia Kłak, Marina V. Kirillova, Piotr Smoleński |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Chemistry Oxide chemistry.chemical_element Atmospheric temperature range 010402 general chemistry 01 natural sciences Magnetic susceptibility Copper Article 0104 chemical sciences Catalysis Inorganic Chemistry Crystallography chemistry.chemical_compound Delocalized electron Ferromagnetism Physical and Theoretical Chemistry Natural bond orbital |
| Zdroj: | Inorganic Chemistry |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.1c00868 |
| Popis: | This work describes an unexpected generation of a new 3D metal–organic framework (MOF), [Cu4(μ-Cl)6(μ4-O)Cu(OH)2(μ-PTA=O)4]n·2nCl-EtOH·2.5nH2O, from copper(II) chloride and 1,3,5-triaza-7-phosphaadamantane 7-oxide (PTA=O). The obtained product is composed of diamandoid tetracopper(II) [Cu4(μ-Cl)6(μ4-O)] cages and monocopper(II) [Cu(OH)2] units that are assembled, via the diamandoid μ-PTA=O linkers, into an intricate 3D net with an nbo topology. Magnetic susceptibility measurements on this MOF in the temperature range of 1.8–300 K reveal a ferromagnetic interaction (J = +20 cm–1) between the neighboring copper(II) ions. Single-point DFT calculations disclose a strong delocalization of the spin density over the tetranuclear unit. The magnitude of exchange coupling, predicted from the broken-symmetry DFT studies, is in good agreement with the experimental data. This copper(II) compound also acts as an active catalyst for the mild oxidation and carboxylation of alkanes. The present study provides a unique example of an MOF that is assembled from two different types of adamantoid Cu4 and PTA=O cages, thus contributing to widening a diversity of functional metal–organic frameworks. A unique 3D MOF composed of adamantoid tetracopper(II) and aminophosphine oxide blocks was assembled and fully characterized, and its magnetic and catalytic properties were investigated. |
| Databáze: | OpenAIRE |
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