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

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

Creative Commons Attribution 4.0 License
This work is licensed under a Creative Commons Attribution 4.0 License.

Language

English

Format

application/pdf

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