Document Type
Article
Publication Date
11-30-2016
Keywords
Aromaticity, Planar molecules, 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 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.
Publication Title
Nature Communications
Volume
7
Issue
Article number: 13620 (2016)
DOI
10.1038/ncomms13620
Required Publisher's Statement
This article was published with a Creative Commons Attribution license. Nature Communications is part of Springer Nature
Link to publisher's version of the article: https://www.nature.com/articles/ncomms13620
Recommended Citation
Ryo Nozawa, Hiroko Tanaka, Won-Young Cha, Yongseok Hong, Ichiro Hisaki, Soji Shimizu, Ji-Young Shin, Tim Kowalczyk, Stephan Irle, Dongho Kim, Hiroshi Shinokubo (2016) Stacked antiaromatic porphyrins. Nat. Commun. 7, 13620.
Subjects - Topical (LCSH)
Aromaticity (Chemistry); Porphyrins
Genre/Form
articles
Type
Text
Rights
Copying of this document in whole or in part is allowable only for scholarly purposes. It is understood, however, that any copying or publication of this document for commercial purposes, or for financial gain, shall not be allowed without the author’s written permission.
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.
Language
English
Format
application/pdf
