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Stacked antiaromatic porphyrins.

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 ?-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 ?-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 ?-systems on the basis of intermolecular orbital interactions.

SUBMITTER: Nozawa R

PROVIDER: S-EPMC5141365 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Stacked antiaromatic porphyrins.

Nozawa Ryo R Tanaka Hiroko H Cha Won-Young WY Hong Yongseok Y Hisaki Ichiro I Shimizu Soji S Shin Ji-Young JY Kowalczyk Tim T Irle Stephan S Kim Dongho D Shinokubo Hiroshi H

Nature communications 20161130

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 ...[more]

PMID: 27901014

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