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

doi:10.1038/ncomms13620

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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84 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 language	English
Article number	13620
Journal	Nature communications
Volume	7
DOIs	https://doi.org/10.1038/ncomms13620
Publication status	Published - Nov 30 2016

All Science Journal Classification (ASJC) codes

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

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10.1038/ncomms13620

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title = "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 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.",

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

note = "Funding Information: This work was supported by the Grant-in-Aid for Scientific Research on Innovative Areas (2601): p-System Figuration (JSPS KAKENHI grant numbers JP26102003 (to H.S.), JP15H00998 (to I.H.) and JP15H01001 (to S.S.) and by the Program for Leading Graduate Schools 'Integrative Graduate Education and Research in Green Natural Sciences' from MEXT, Japan. Crystallographic data were collected at the SPring-8 beam line BL38B1 with approval of the JASRI (proposal nos. 2015B1397 and 2016A1121). H.S. acknowledges the Asahi Glass Foundation for financial support. Research at Yonsei University was supported by the Samsung Science and Technology Foundation (SSTF-BA1402-10). Publisher Copyright: {\textcopyright} The Author(s) 2016.",

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AU - Nozawa, Ryo

AU - Tanaka, Hiroko

AU - Cha, Won Young

AU - Hong, Yongseok

AU - Hisaki, Ichiro

AU - Shimizu, Soji

AU - Shin, Ji Young

AU - Kowalczyk, Tim

AU - Irle, Stephan

AU - Kim, Dongho

AU - Shinokubo, Hiroshi

N1 - Funding Information: This work was supported by the Grant-in-Aid for Scientific Research on Innovative Areas (2601): p-System Figuration (JSPS KAKENHI grant numbers JP26102003 (to H.S.), JP15H00998 (to I.H.) and JP15H01001 (to S.S.) and by the Program for Leading Graduate Schools 'Integrative Graduate Education and Research in Green Natural Sciences' from MEXT, Japan. Crystallographic data were collected at the SPring-8 beam line BL38B1 with approval of the JASRI (proposal nos. 2015B1397 and 2016A1121). H.S. acknowledges the Asahi Glass Foundation for financial support. Research at Yonsei University was supported by the Samsung Science and Technology Foundation (SSTF-BA1402-10). Publisher Copyright: © The Author(s) 2016.

PY - 2016/11/30

Y1 - 2016/11/30

N2 - 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.

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Stacked antiaromatic porphyrins

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