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Lanthanide metals in the boron cages: Computational prediction of M@B n (M = Eu, Gd; n = 38, 40)
Author(s) -
Xi Cong,
Yang Le,
Liu Chang,
You Peng,
Li Lanlan,
Jin Peng
Publication year - 2018
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25576
Subject(s) - lanthanide , endohedral fullerene , boron , density functional theory , chemistry , fullerene , metal , crystallography , spins , electron , spectral line , homo/lumo , computational chemistry , atomic physics , materials science , molecule , physics , condensed matter physics , ion , organic chemistry , astronomy , quantum mechanics
Endohedral metalloborofullerenes (EMBFs) are novel boron analogues of the famous endohedral metallofullerenes (EMFs). Many EMBFs have been proposed by theoretical calculations thus far. However, in sharp contrast to EMFs, which trap most of the lanthanides with f electrons inside the cages, the corresponding lanthanide‐based EMBFs have never been reported. In this work, the encapsulation of Eu and Gd in the B 38 and B 40 fullerenes was studied by means of density functional theory calculations. Our results revealed that Gd@B 38 ( 9 A), Eu@B 40 ( 8 B 2 ), and Gd@B 40 ( 7 A″) all favor the endohedral configuration, and the electronic structures can be described as Gd 3+ @ B 38 3 − , Eu 2+ @ B 40 2 − , and Gd 3+ @ B 40 3 −with jailed f electron spins. The large binding energies and sizable HOMO–LUMO gaps suggest that they may be achieved experimentally. They feature σ and π double aromaticity, and their excellent stabilities were confirmed by the Born–Oppenheimer molecular dynamics simulations. Finally, the infrared and UV/vis spectra were simulated to assist experimental characterization.