Metalloborospherenes with the stabilized classical fullerene-like borospherene B₃₆as electric field manipulated second-order nonlinear optical switches

Abstract

For a new challenge of stabilizing a classical fullerene-like borospherene composed of five- and six-membered rings, we take the lead to theoretically present a novel exohedral metalloborospherene Mg12Li8&B36 molecule (D6h)....

Metalloborospherenes with a Stabilized Classical Fullerene-like Borospherene B40 Act as Nonlinear Optical Switches, Electron Reservoirs, Molecular Capacitors, and Molecular Reactors

“…However, due to the electron-deficient nature of the boron atom, it has 54 imaginary frequencies (see Table ) and is unstable. In a previous work, the classical fullerene-like borospherene D 6h B 36 is stabilized in the exohedral metalloborospherene D 6h Mg 12 Li 8 &B 36 by η 5 -Mg and η 6 -Li atoms capping the pentagon and hexagon faces of the borospherene, respectively . We also try to stabilize T d B 40 in this way (12 η 5 -Mg and 10 η 6 -Li) (see Figure S3).…”

“…Molecular electron reservoirs are compounds that store and transfer electrons stoichiometrically or catalytically without decomposition, for example, organoiron electron–reservoir complexes, an iron–iron hydrogenase, and spherical molecules. , The electron–reservoir system can be considered to be a Green redox system. , Mg 10 Li 12 &B 40 and its endohedral molecules as well as endo-cage isomers have multilayered charge distributions, bringing unusual electronic properties. From Tables and , it is observed that due to the loosely bound multi-excess electrons of the outer layer, Mg 10 Li 12 &B 40 and its endohedral molecules as well as endo-cage isomers have lower VIP values of 3.51–4.22 eV than the K atom (4.34 eV), exhibiting a strong electron-donating ability of the alkali metal.…”

“…In previous works, we have predicted that the smallest classical fullerene-like borospherene B 20 with only 12 pentagons can be effectively stabilized by 12 η 5 -Mg atoms as electron donors . Furthermore, the classical fullerene-like borospherene B 36 with 12 pentagons and 8 hexagons can also be effectively stabilized by 12 η 5 -Mg atoms and 8 η 6 -Li atoms . Such unique systems can serve as electron reservoirs due to the electron-accepting and -donating characters.…”

“…53 Furthermore, the classical fullerene-like borospherene B 36 with 12 pentagons and 8 hexagons can also be effectively stabilized by 12 η 5 -Mg atoms and 8 η 6 -Li atoms. 54 Such unique systems can serve as electron reservoirs due to the electron-accepting and -donating characters. Additionally, they can also serve as efficient external electric field-manipulated nonlinear optical (NLO) switches in NLO property research studies.…”

“…where n is the number of atoms involved in the calculation, and P ̂is the permutation operator that generates all possible permutation sequences. 54 We also try to stabilize T d B 40 in this way (12 η 5 -Mg and 10 η 6 -Li) (see Figure S3). However, the obtained Mg 12 Li 10 &B 40 structure is less stable, which is reflected by the smaller lowest vibrational frequency of 24 cm −1 and smaller HOMO−LUMO gap value of 0.60 eV (see Table S5).…”