Actinide endohedral inter-metalloid clusters of the group 15 elements

Inter-metalloid clusters in Zintl chemistry have been extensively studied due to the unique electronic structures and potential applications. In this work, we explored a series of actinide endohedral inter-metalloid clusters of the group 15 elements [An@Bi12]4- (An = Th-U) and [An@Sb12]4- using dens...

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Published in:Physical chemistry chemical physics : PCCP 2024
Main Authors: Zhang, Nai-Xin, Wang, Congzhi, Lan, Jianhui, Wu, Qun-Yan, Shi, Weiqun
Format: Article
Language:English
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Summary:Inter-metalloid clusters in Zintl chemistry have been extensively studied due to the unique electronic structures and potential applications. In this work, we explored a series of actinide endohedral inter-metalloid clusters of the group 15 elements [An@Bi12]4- (An = Th-U) and [An@Sb12]4- using density functional theory (DFT). [Th@Bi12]4- and [U@Bi12]4- exhibit Cs symmetry, while [Pa@Bi12]4- and [An@Sb12]4- (An = Th-U) have C1 structures. Bonding analyses such as bond order, molecular orbitals (MO) and quantum theory of atoms in molecules (QTAIM) show the covalent An-Bi/An-Sb bonding in the clusters. All these clusters are highly stable according to the studied formation reactions, and may be accessible experimentally. Compared with [An@Bi12]4-, [An@Sb12]4- possess stronger bonding interactions, mainly arose from the higher electrostatic interaction energy. For clusters with the same group 15 elements, the bonding interactions increase gradually from Th to U, which is mainly determined by the covalent interactions of the An-Bi/An-Sb bonding. This work is expected to provide potential avenues for the construction of robust inter-metalloid clusters of the group 15 elements.
ISSN:1463-9076
1463-9084
DOI:10.1039/D4CP02546F