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Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study

Density functional theory calculations of magnetically induced current densities have revealed high diatropic ring currents in unsubstituted isocorrole consistent with homoaromatic character. An examination of the Kohn-Sham molecular orbitals showed clear evidence of homoconjugative interactions in...

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Autores principales: Foroutan-Nejad, Cina, Larsen, Simon, Conradie, Jeanet, Ghosh, Abhik
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6086901/
https://www.ncbi.nlm.nih.gov/pubmed/30097587
http://dx.doi.org/10.1038/s41598-018-29819-3
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author Foroutan-Nejad, Cina
Larsen, Simon
Conradie, Jeanet
Ghosh, Abhik
author_facet Foroutan-Nejad, Cina
Larsen, Simon
Conradie, Jeanet
Ghosh, Abhik
author_sort Foroutan-Nejad, Cina
collection PubMed
description Density functional theory calculations of magnetically induced current densities have revealed high diatropic ring currents in unsubstituted isocorrole consistent with homoaromatic character. An examination of the Kohn-Sham molecular orbitals showed clear evidence of homoconjugative interactions in four occupied π-type molecular orbitals as well as in the LUMO. Remarkably, substituents at the saturated meso position were found to exert a dramatic influence on the overall current density pattern. Thus, whereas bis(trimethylsilyl)-substitution strongly enhanced the peripheral diatropic current (consistent with enhanced homoaromaticity), difluoro-substitution engendered a strong, net paratropic current (consistent with antihomoaromaticity). In this respect, isocorroles stand in sharp contrast to benzenoid aromatics, for which substituents typically exert a small influence on the current density distribution.
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spelling pubmed-60869012018-08-16 Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study Foroutan-Nejad, Cina Larsen, Simon Conradie, Jeanet Ghosh, Abhik Sci Rep Article Density functional theory calculations of magnetically induced current densities have revealed high diatropic ring currents in unsubstituted isocorrole consistent with homoaromatic character. An examination of the Kohn-Sham molecular orbitals showed clear evidence of homoconjugative interactions in four occupied π-type molecular orbitals as well as in the LUMO. Remarkably, substituents at the saturated meso position were found to exert a dramatic influence on the overall current density pattern. Thus, whereas bis(trimethylsilyl)-substitution strongly enhanced the peripheral diatropic current (consistent with enhanced homoaromaticity), difluoro-substitution engendered a strong, net paratropic current (consistent with antihomoaromaticity). In this respect, isocorroles stand in sharp contrast to benzenoid aromatics, for which substituents typically exert a small influence on the current density distribution. Nature Publishing Group UK 2018-08-10 /pmc/articles/PMC6086901/ /pubmed/30097587 http://dx.doi.org/10.1038/s41598-018-29819-3 Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Foroutan-Nejad, Cina
Larsen, Simon
Conradie, Jeanet
Ghosh, Abhik
Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title_full Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title_fullStr Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title_full_unstemmed Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title_short Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
title_sort isocorroles as homoaromatic nir-absorbing chromophores: a first quantum chemical study
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6086901/
https://www.ncbi.nlm.nih.gov/pubmed/30097587
http://dx.doi.org/10.1038/s41598-018-29819-3
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