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6934488 
Journal Article 
Electronic and structural relations between solid CaB6 and the molecular dianion B6H6(2-): A computational study 
Oliva-Enrich, JM; Alcoba, DR; Ona, OB; Lain, L; Torre, A; Jiao, Y; Ma, Bo; Chen, Z; Wu, Wei; , 
2020 
1 
Solid State Sciences
ISSN: 1293-2558
EISSN: 1873-3085 
ELSEVIER 
AMSTERDAM 
WOS:000531485500004 
By means of the isolobality concept between a hydrogen atom and the radical dianion [B6H5 center dot](2-) derived from an extraction of a hydrogen atom in the dianion [B6H6](2-), forming part of the K-2(B6H6) structure, we rationalize the 3D boron skeleton architecture in the solids CaB6 and KB6. The above statement is supported by electronic structure computations based on the Electron Localisation Function (ELF) in the dianion [B6H6](2-) and radical anion [B6H5 center dot](2-). Valence-Bond (VB) theory is also used in the study of the B-B sigma bond connecting the octahedra in the CaB6 structure, with the model dimer [(H5B5)B-B(B5H5)](4-). Quantum-chemical geometry optimizations of clusters extracted from the CaB6 solid structure show the analogies between molecular chemistry and solid-state chemistry: In the same way as benzene is the building block of graphene and graphite, the anion [B6H6](2-) is the building block of CaB6 provided every hydrogen atom in [B6H6](2-) is connected to a further [(B-center dot)(6)](2-) octahedron in the three directions of the 3D space, and every void at the Ca positions is embedded with two electrons.