Double aromaticity of the B fullerene: induced magnetic field analysis of π and σ delocalization in the boron cavernous structure

• Published in: Physical chemistry chemical physics : PCCP 2019-09, Vol.21 (36), p.2232-2238
• Main Authors: Charistos, Nickolas D, Muñoz-Castro, Alvaro
• Format: Article
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c9cp04223g

The induced magnetic field of B 40 was dissected into contributions from π, σ and core electrons revealing the origins for the formation of the strong long range shielding response characterizing the spherical aromatic nature of the cavernous D 2d structure. Our analysis showed the complementary role of π and σ orbitals for the formation of the global shielding cone, with weak π contributions at a long range and strong σ contributions inside the cage, supporting the molecule as double aromatic with weak π and strong σ delocalization. Similar local variations of both π and σ magnetic responses were identified portraying peripheral diatropic and local paratropic currents. The weak π aromaticity is explained on the basis of symmetry rules pertaining to its electronic structure which forbid small gap paratropic rotational excitations. B 40 enables the formation of a strong long range shielding response under different orientations, characterizing the spherical aromatic nature of the cavernous D 2d structure, which was dissected to contributions from π, σ and core electrons.