Isocorroles as Homoaromatic NIR-Absorbing Chromophores: A First Quantum Chemical Study
| Authors | |
|---|---|
| Year of publication | 2018 |
| Type | Article in Periodical |
| Magazine / Source | Scientific reports |
| MU Faculty or unit | |
| Citation | |
| Web | https://www.nature.com/articles/s41598-018-29819-3.pdf |
| Doi | http://dx.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. |
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