Construction of the Largest Metal-Centered Double-Ring Tubular Boron Clusters Based on Actinide Metal Doping

Abstract

Metal doping has been considered to be an effective approach to stabilize various boron clusters. In this work, we constructed a series of largest metal-centered double-ring tubular boron clusters An@B 24 (An = Th, Pa, Pu, and Am). Extensive global minimum structural searches combined with density functional theory predicted that the global minima of An@B 24 (An = Th, Pu, and Am) are double-ring tubular structures. Formation energy analysis indicates that these boron clusters are highly stable, especially for Th@B 24 and Pa@B 24 . Detailed bonding analysis shows that the significant stability of An@B 24 is determined by the covalent character of the An−B bonding, which stems from the interactions of An 5f and 6d orbitals and B 2p orbitals. These results show that actinide metal doping is a feasible route to construct stable large metal-centered doublering tubular boron clusters, offering the possibility to design boron nanomaterials with special physiochemical properties.

Theoretical investigations on the structures and electronic and optical properties of neutral and anionic M2-doped B24clusters (M = Li, Na, and K)

“…Early research found that B 24 possesses a double-ring tubular shape, and B 24 − exhibits a planar structure. After adding a single transition or actinide metal atom, 23,33,34 the doped isomers undergo drastic structural changes with respect to the corresponding boron clusters. Walking through the lowest energy structures of all doped systems, the doped single-metal atom is endohedrally incorporated at the interior of the cage, tubular and quasi-planar skeleton.…”

“…52–54 In particular, due to its better alignment with the experimental results for alkali metal-doped boron clusters, the PBE0 functional was included in the present work. 32,34 More importantly, the spin multiplicity is included, and no imaginary frequencies are validated. In addition, in order to check that the calculated results are independent of the functional and basis set, the lowest and low-lying isomers of M 2 B 24 0/− (M = Li, Na, and K) clusters are calculated at the DFT-D3/6-311+G(d) level 55 and at the single-point CCSD(T)/def2-TZVP level based on the geometry optimization at the PBE0/6-311+G(d) level in the ORCA program.…”

“…Recently, Wang et al 's groups focused on the geometric structure and bonding properties of An@B 24 (An = Th, Pa, Pu, and Am) clusters. 34 A double-ring tubular framework is identified by the global minimum structure search and frequency calculations. In addition, analyses of An–B bonding show that the stability of An@B 24 is determined by the covalent character.…”

High Coordination Numbers of Actinides (An) in AnC13+ Rings (An = Th and U)

“…QTAIM analyses were performed to further explore the nature of the bonds in the ThC 13 + and UC 13 + cluster cations. The QTAIM metrics are particularly useful in f-element chemistry. − The molecular graphs of the ThC 13 + and UC 13 + clusters, as well as the QTAIM metrics, ρ­( r ), ∇ 2 ρ­( r ), H ( r ), and − G ( r )/ V ( r ), at the bond critical point (BCP) corresponding to the C–C and C–An bonds are shown in Figure . According to a general criterion of QTAIM, the interactions with ρ­( r ) > 0.2 au and ∇ 2 ρ­( r ) < 0 are covalent in nature, whereas ρ­( r ) < 0.1 au indicates a type of ionic interaction.…”

Geometric and electronic structures of medium-sized boron clusters doped with plutonium

“…A series of actinide (An) doped boron clusters were reported recently, such as the half-sandwich structure AnB 12 (An = Th to Cm) [46], the actinide-embedded boronspheres AnB n (An = U and Th; n = 36, 38, and 40) [44,47], the chiral actinide-endohedral boron spheres (AcB 39 0/2+ and ThB 39 0/3+ ) [48] and the boron molecular drums AnB 20 (An = U, Np and Pu) [49]. In addition, Wang et al [50] constructed a series of metal-centered bicyclic tubular clusters AnB 24 (An = Th, Pa, Pu, and Am), which may be the largest metal-centered boron clusters with double-ring configuration reported so far. Therefore, An-doping may be a viable way for stabilizing the large-sized double boron ring, providing the possibility to design boron-based nanomaterials.…”