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Cage-like La4B24 and Core-Shell La4B290/+/− : perfect spherically aromatic tetrahedral metallo-borospherenes

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Abstract

Cage-like and core-shell metallo-borospherenes exhibit interesting structures and bonding. Based on extensive global searches and first-principles theory calculations, we predict herein the perfect tetrahedral cage-like Td La4B24 (1) and core-shell Td La4B29 (2), Td La4B29+ (3), and Td La4B29− (4) which all possess the same geometrical symmetry as their carbon fullerene counterpart Td C28, with four equivalent interconnected B6 triangles on the cage surface and four nona-coordinate La centers in four conjoined η9-B9 rings. In these tetra-La-doped boron complexes, La4[B@B4@B24]0/+/− (2/3/4) in the structural motif of 1 + 4 + 28 contain a B-centered tetrahedral Td B@B4 core in a La-decorated tetrahedral La4B24 shell, with the negatively charged tetra-coordinate B− at the center being the boron analog of tetrahedral C in Td CH4 (B− ~ C). Detailed orbital and bonding analyses indicate that these Td lanthanide boride complexes are spherically aromatic in nature with a universal La--B9 (d-p) σ and (d-p) δ coordination bonding pattern. The IR, Raman, and UV-Vis or photoelectron spectra of these novel metallo-borospherenes are computationally simulated to facilitate their spectral characterizations.

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The work was supported by the National Natural Science Foundation of China (21720102006 and 21973057 to S.-D. Li).

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  1. Institute of Molecular Science, University of Shanxi, Taiyuan, 030006, China

    Xiao-Qin Lu, Cai-Yue Gao, Zhihong Wei & Si-Dian Li

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Z. H. Wei and S. D. Li designed the project and X. Q. Lu and C. Y. Gao performed the calculations. All the authors participate in the discussion and preparation of the manuscript.

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Lu, XQ., Gao, CY., Wei, Z. et al. Cage-like La4B24 and Core-Shell La4B290/+/− : perfect spherically aromatic tetrahedral metallo-borospherenes. J Mol Model 27, 130 (2021). https://doi.org/10.1007/s00894-021-04739-8

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