Theoretical Studies of Divalent Actinide Complexes AnB8

doi:10.6023/A25080276

Abstract

Due to the electron-deficient characteristics of boron, boron clusters exhibit a variety of structures with size changes, and the doping of different metal atoms can further enrich the structures and properties of boron clusters. We investigated a series of actinide metal-doped boron clusters AnB₈ (An=Ac, Th, Am, Cm) by using the global minimum structural searches and density functional theory (DFT) methods. For each isomer, different spin states were considered at the PBE0/6-311＋G*/RECP and TPSSH/6-311＋G*/RECP theoretical levels. It is found that each AnB₈ cluster possesses two configurations, half-sandwich and chair-like structures. Except for ThB₈, the half-sandwich structures of AcB₈, AmB₈ and CmB₈ are more stable, while the energy difference between the two structures of ThB₈ is small, indicating that both may coexist in experiments. The half-sandwich structures of AcB₈, ThB₈, AmB₈, and CmB₈ correspond to doublet, singlet, octet, and nonet states, respectively. ThB₈ is a closed-shell singlet system, in which the electronic configuration of the Th element may be [Rn]6d². Voronoi deformation density (VDD) and Hirshfeld charges suggest that charge flows from the actinide elements to the boron ligands. The half-sandwich structures of these boron clusters are stable M^II[${B}_{8}^{2-}$]-type divalent actinide complexes. Molecular orbital (MO) analysis shows that the An—B bonding orbitals of AcB₈ and ThB₈ mainly originate from An 6d orbitals, while those of AmB₈ and CmB₈ are primarily contributed by An 5f orbitals. Other analyses of bonding properties also indicate that there exist covalent interactions between An and B atoms in all complexes, and ThB₈has stronger covalent interactions. For these AnB₈ complexes, the ${B}_{8}^{2-}$ ligands show double aromaticity features, which have six delocalized σ electrons and six delocalized π electrons. According to dissociation energy analysis, all the AnB₈ complexes are highly stable, especially ThB₈. These results indicate that the ${B}_{8}^{2-}$ ligands are capable of stabilizing the divalent actinides.

Key words: boron clusters, metal doping, actinides, density functional theory, global minimum structural search

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Naixin Zhang, Weiqun Shi, Congzhi Wang. Theoretical Studies of Divalent Actinide Complexes AnB₈[J]. Acta Chimica Sinica, 2025, 83(12): 1523-1529.

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Fig. & Tab. 9

Figure 1. The optimized geometrical structures and relative energies of AnB8 at the PBE0/6-311＋G*/RECP level of theory (The brackets represent the relative energies calculated by the TPSSH method, kJ/mol). The pink spheres represent the B atom, the blue, orange, green, and purple spheres represent the Ac, Th, Am, and Cm atoms, respectively

硼团簇	自旋态	⟨S²⟩_{计算值-理论值}	自旋密度 ρ_An	键长/nm
硼团簇	自旋态	⟨S²⟩_{计算值-理论值}	自旋密度 ρ_An	An—B₁	An—B_a
AcB₈	双重态	0.00	0.77	0.2750	0.3017
ThB₈	单重态	—	—	0.2485	0.2729
AmB₈	八重态	0.02	7.14	0.2573	0.2882
CmB₈	九重态	0.03	8.10	0.2588	0.2849

Table 1. Spin states, the differences between the calculated and theoretical spin contamination ⟨S2⟩计算值-理论值, Mulliken atomic spin densities (ρAn), and average An—B1 and An—Ba average bond distances (the B1 atom is the central boron atom of the boron ring, while the Ba atoms are the peripheral boron atoms of the boron ring) for AnB8 at the PBE0/6-311＋G*/RECP level of theory

硼团簇	原子电荷/a.u.		WBIs		SOMO-LUMO 能隙/eV
硼团簇	VDD	Hirshfeld	An—B₁	An—B_a	α	β
AcB₈	0.743	0.796	0.620	0.421	1.20	3.45
ThB₈	0.746	0.723	0.611	0.516	1.49	—
AmB₈	0.766	0.807	0.638	0.346	2.91	3.50
CmB₈	0.607	0.636	0.631	0.425	2.16	3.81

Table 2. The charge analysis of An, WBIs of the An-B bonds, and the SOMO-LUMO gap (eV) of AnB8 at the PBE0/6-311＋G*/RECP level of theory

Figure 2. The QTAIM analysis of AcB8, AmB8, CmB8 (left) and ThB8 (right) at the PBE0/6-311＋G*/RECP level of theory. Red points represent bond critical points, grey lines represent bond paths, and green points represent ring critical points

硼团簇	ρ	H	∇²ρ	ELF	DI_total
AcB₈	0.03987	－0.00481	0.07581	0.24085	2.387
ThB₈	0.06165	－0.01692	0.06650	0.40489	3.628
AmB₈	0.04167	－0.00736	0.11279	0.14418	1.800
CmB₈	0.04180	－0.00726	0.11792	0.13616	2.226

Table 3. The QTAIM analysis (a.u.) of AnB8 at the PBE0/6-311＋G*/RECP level of theory

Figure 3. MOs of AmB8 at the PBE0/6-311＋G*/RECP level of theory

Figure 4. AdNDP analysis of AmB8

反应方程	解离能
AcB₈→Ac^2＋＋${B}_{8}^{2-}$	2055.6
ThB₈→Th^2＋＋${B}_{8}^{2-}$	2384.0
AmB₈→Am^2＋＋${B}_{8}^{2-}$	1988.2
CmB₈→Cm^2＋＋${B}_{8}^{2-}$	2190.7

Table 4. The dissociation energy (kJ/mol) of AnB8 at the PBE0/6-311＋G*/RECP level of theory

Figure 5. The infrared spectra of AmB8 and CmB8

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二价锕系配合物AnB₈的理论研究

Theoretical Studies of Divalent Actinide Complexes AnB₈

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二价锕系配合物AnB8的理论研究