Stacked antiaromatic porphyrins

Ryo Nozawa, Hiroko Tanaka, Won Young Cha, Yongseok Hong, Ichiro Hisaki, Soji Shimizu, Ji Young Shin, Tim Kowalczyk, Stephan Irle, Dongho Kim, Hiroshi Shinokubo

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47 Citations (Scopus)

Abstract

Aromaticity is a key concept in organic chemistry. Even though this concept has already been theoretically extrapolated to three dimensions, it usually still remains restricted to planar molecules in organic chemistry textbooks. Stacking of antiaromatic π-systems has been proposed to induce three-dimensional aromaticity as a result of strong frontier orbital interactions. However, experimental evidence to support this prediction still remains elusive so far. Here we report that close stacking of antiaromatic porphyrins diminishes their inherent antiaromaticity in the solid state as well as in solution. The antiaromatic stacking furthermore allows a delocalization of the π-electrons, which enhances the two-photon absorption cross-section values of the antiaromatic porphyrins. This feature enables the dynamic switching of the non-linear optical properties by controlling the arrangement of antiaromatic π-systems on the basis of intermolecular orbital interactions.

Original languageEnglish
Article number13620
JournalNature communications
Volume7
DOIs
Publication statusPublished - 2016 Nov 30

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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    Nozawa, R., Tanaka, H., Cha, W. Y., Hong, Y., Hisaki, I., Shimizu, S., Shin, J. Y., Kowalczyk, T., Irle, S., Kim, D., & Shinokubo, H. (2016). Stacked antiaromatic porphyrins. Nature communications, 7, [13620]. https://doi.org/10.1038/ncomms13620