Journal
INORGANIC CHEMISTRY
Volume 60, Issue 12, Pages 8984-8989Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c00886
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Funding
- National Natural Science Foundation of China [21806118, 21790374, 21976014, U1930402]
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The study presented the synthesis, crystal structure, spectroscopic analyses, and theoretical calculations of the first trivalent plutonium crown ether inclusion complex Pu-III-18C6. It was found that the plutonium atom is completely encapsulated within the cavity of the 18-crown-6, forming a distorted geometric structure, with weak Pu-O dative bond confirmed by theoretical evaluation. This work may enhance the understanding of host-guest interactions between trivalent transuranic elements and macrocyclic ligands.
We report the synthesis, single-crystal structure, solid-state ultraviolet-visible-near-infrared spectroscopy, and theoretical calculations on the first trivalent plutonium crown ether inclusion complex, [(H3O)(18-crown-6)][Pu(H2O)(4)(18-crown-6)](ClO4)(4)center dot 2(H2O) (denoted as Pu-III-18C6). Single-crystal X-ray diffraction reveals that Pu-III-18C6 crystallizes in the orthorhombic space group of Pccn, which is assembled by independent ionic pairs including [Pu(H2O)(4)(18-crown-6)](3+), [(H3O)(18-crown-6)](+), and perchlorate anions. The plutonium atom is fully encapsulated within the cavity of the 18-crown-6, generating a distorted bicapped square antiprism geometry. The theoretical evaluation confirms that weak Pu-O dative bond is involved between Pu-III ions with 18-crown-6. This work may deepen the understanding of the host-guest interactions between trivalent transuranic and macrocyclic ligands.
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