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

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Authors	FOROUTANNEJAD Cina LARSEN Simon CONRADIE Jeanet GHOSH Abhik
Year of publication	2018
Type	Article in Periodical
Magazine / Source	Scientific reports
MU Faculty or unit	Central European Institute of Technology
Citation
web	https://www.nature.com/articles/s41598-018-29819-3.pdf
Doi	https://doi.org/10.1038/s41598-018-29819-3
Keywords	NIR dye; Electronic Current; Porphyrinoids; Spectroscopy
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 p-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.
Related projects:	CERIT Scientific Cloud