Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB₂₄ (M = Sc, V, and Mn)

Abstract

A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB24 (M = Sc, V, and Mn) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the VB24 and MnB24 clusters correspond to cage structures. Interestingly, the global minima obtained for the ScB24 cluster tend to a three-ring tubular structure. Population analyses and valence electron density analyses reveal that partial electrons on transition-metal atoms transfer to boron atoms. The localized orbital locator of MB24 (M = Sc, V, and Mn) indicates that the electron delocalization of ScB24 is stronger than that of VB24 and MnB24, and there is no obvious covalent bond between doped metals and B atoms. The spin density and spin population analyses reveal that MB24 (M = Sc, V, and Mn) have different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The calculated spectra indicate that MB24 (M = Sc, V, and Mn) has meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.

Structural Evolution and Electronic Properties of Selenium-Doped Boron Clusters SeBn0/− (n = 3–16)

“…Co and Rh atom-doped boron clusters MB 12 (M = Co and Rh) can lead to the quasi-planar B 12 form, a semi-sandwich configuration [ 3 , 24 ]. Neutral B 24 has a double-ring configuration [ 39 ], while TiB 24 and ScB 24 have a cage configuration and three-ring tubular structure, respectively, after adding one Sc or Ti atom [ 41 , 42 ]. Anionic B 24 − has a quasi-planar structure [ 7 ], while TiB 24 − and VB 24 − have a cage configuration after adding one Ti or V atom [ 43 ].…”

Structural Evolution and Electronic Properties of Two Sulfur Atom-Doped Boron Clusters

“…In recent years, researchers have mainly focused on the structure and properties of boron clusters doped with metal atoms. 15,17−19,24−39 − , 3,24,423,24,42 adjust double-ring tubular B 24 to cagedoped boron clusters (TiB 24 ) and three-ring tubular doped boron clusters (ScB 24 ), 40,43,44 adjust quasi-planar B 24 − to cagedoped boron clusters (TiB 24 − and VB 24 − ). 7,45 In addition, doped borospherenes MB 40 (M = Li, Na, or K) are expected to be applied in nonlinear optical materials, 18 doped borospherenes CoB 40 and MB 40 (M = Sc, Ti) are expected to be applied in molecular devices and hydrogen storage materials, 15,17,19,26 and Co-and Rh-doped boron clusters MB 12 − (M = Co, Rh) can improve chemical activity.…”

Designing a Four-Ring Tubular Boron Motif through Metal Doping

“…− and MnB 16 − ) 8,9 are the record holders for 1D and 2D coordination numbers, respectively. 10 In addition, metal-centered cages (MB 24 ; M = Mo, V, Mn), 11,12 half-sandwich- 13 and inverse-sandwich-type structures (Ln 2 B n − , where n = 7−9), 14,15 and spherical trihedra 16 all strongly reflect the significant effect of metal doping on novel structural and electronic properties and unique bonding interactions between doped metals and boron motifs.…”

“…The planar/quasi-planar, tubular, and cage structures and their regular structural transition of planar-to-tubular-to-cage (2D-to-3D) have vividly unveiled the capacity of boron to form unusual geometries and electron-delocalized bonding. − It is noteworthy that much more intriguing geometries and chemical bonding, which usually do not exist in pure boron species, have further been induced by doping metals into boron clusters. − For instance, transition-metal-centered monocyclic rings in M©B 10 – (M = Nb, Ta) and metal-centered tubular structures (CoB 16 – and MnB 16 – ) , are the record holders for 1D and 2D coordination numbers, respectively . In addition, metal-centered cages (MB 24 ; M = Mo, V, Mn), , half-sandwich- and inverse-sandwich-type structures (Ln 2 B n – , where n = 7–9), , and spherical trihedra all strongly reflect the significant effect of metal doping on novel structural and electronic properties and unique bonding interactions between doped metals and boron motifs.…”

“…While some tubular boron or metal-doped boron clusters have been obtained as discussed above, most of them are two-ring tubular cases, and their higher-ring analogues are very scarce. − A few three-ring tubular examples can be found in B 27 + , B 42 , Li 2 B 24 , ScB 24 , and PrB n ( n = 28, 30, 36) clusters . Hence, the question remains as to whether higher-ring tubular boron clusters exist!…”