Ghorai, S and Jemmis, ED (2022) From a Möbius-aromatic interlocked Mn2B10H10 wheel to the metal-doped boranaphthalenes M2@B10H8 and M2B5 2D-sheets (M = Mn and Fe): a molecules to materials continuum using DFT studies. In: Chemical Science, 13 . pp. 8968-8978.
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Abstract
The inherent tendency of BR fragments to undergo coupling is utilized to predict M2B10H10 and M2@B10H8 complexes (where M = Mn and Fe). Electronic structure analysis of Mn2B10H10 (7) shows that the metal d-orbitals stabilize the interlocked boron wheel structure, forming an unprecedented geometrical pattern with Möbius aromaticity. The two additional electrons in Fe2@B10H10 (8) stabilize a twisted [10]boraannulene structure. The removal of 2H from 7 and 8 leads to the planar structures Mn2@B10H8 (11) and Fe2@B10H8 (10), respectively. The stability of the planar arrangements is due to multicentered (σ + π) bonding, where π-donation occurs from the M2 (M = Fe and Mn) unit to the borocyclic unit. The presence of 10π electrons in M2@B10H8 relates it to naphthalene, having Hückel π-aromaticity. The condensation of naphthalene to graphene in two dimensions suggests the ability to build the different metal boride monolayers FeB5 and Fe2B5, considering Fe2@B10 as the building block, bringing this molecular boron chemistry into the solid state. One of the predicted monolayers, β-Fe2B5, is found to be the global minimum in the planar arrangement based on a USPEX crystal structure search algorithm. Electronic structure analysis further shows that the stabilization mechanism in the molecular building block remains unaltered in the solid state.
| Item Type: | Journal Article |
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| Publication: | Chemical Science |
| Publisher: | Royal Society of Chemistry |
| Additional Information: | The copyright for this article belongs to the Authors. |
| Keywords: | Aromatization; Boron; Chemical bonds; Crystal structure; Electronic structure; Manganese; Manganese compounds; Monolayers; Wheels, Aromaticities; D orbitals; DFT study; Electronic.structure; Geometrical patterns; Metal-doped; Planar structure; Structure analysis; Two-dimensions; �-bonding, Naphthalene |
| Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
| Date Deposited: | 23 Aug 2022 05:23 |
| Last Modified: | 23 Aug 2022 05:23 |
| URI: | https://eprints.iisc.ac.in/id/eprint/76161 |
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