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Muñoz-Castro, Alvaro
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 06/2021, Letnik: 125, Številka: 22Journal Article
The characterized phenyl decorated closo-monocarboranes with variable sizes from 7- to 12-vertex cages, Ph-closo-CB n H n −, n = 6–11, allow us to address the role of the varying size and shape of the carborane cage in dual planar–spherical aromatic species. Our results show the formation of adjacent shielding cone characteristics enabled from both planar and spherical aromatic fragments, despite the different structures of the closo-monocarboranes. Under a field perpendicular to the phenyl ring, both shielding cones are enabled, which overlap at long-range regions, in contrast to other orientations leading to a short-range response from the planar aromatic fragment. Thus, a two- or one-aromatic circuit is enabled selectively within the same molecular unit, by controlling the orientation of the external field. Along with the series, a variable extension of the shielding cone from the carborane cage is observed, which is larger for the −CB11H11 case, decreasing toward −CB6H6, denoting a similar extension from both the planar and spherical aromatic regions at the 4-Ph-closo-4-CB8H8− (4) counterpart. The analysis of such multiple aromatic structures shows that, despite the different sizes and shapes of the closo cages, a similar aromatic behavior remains. In addition, the anisotropy of the induced magnetic field is given graphically, denoting a larger anisotropy for the planar aromatic moiety owing to its two-dimensional structure, which is suggested to discriminate between planar and spherical aromatic fragments within the same molecule.
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