Benzonorcorrole NiII Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion

Takuya Yoshida; Kohtaro Takahashi; Yuki Ide; Ryohei Kishi; Jun Ya Fujiyoshi; Sangsu Lee; Yuya Hiraoka; Dongho Kim; Masayoshi Nakano; Takahisa Ikeue; Hiroko Yamada; Hiroshi Shinokubo

doi:10.1002/anie.201712961

Benzonorcorrole Ni^II Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion

Takuya Yoshida, Kohtaro Takahashi, Yuki Ide, Ryohei Kishi, Jun Ya Fujiyoshi, Sangsu Lee, Yuya Hiraoka, Dongho Kim, Masayoshi Nakano, Takahisa Ikeue, Hiroko Yamada, Hiroshi Shinokubo

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

26 Citations (Scopus)

Abstract

Fused benzene rings to antiaromatic compounds generally improve their stability but attenuate their antiaromaticity. The opposite case is now reported. Ni^II benzonorcorroles were synthesized and the effect of benzo-fusion on the antiaromaticity was elucidated. The benzo-fusion resulted in significant decrease of the HOMO–LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, the introduction of the benzo groups induced singlet diradical character in the antiaromatic porphyrinoid.

Original language	English
Pages (from-to)	2209-2213
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	8
DOIs	https://doi.org/10.1002/anie.201712961
Publication status	Published - 2018 Feb 19

Bibliographical note

Funding Information:
This work was supported by JSPS KAKENHI grants JP26102003 (H.S.), JP15K21721 (H.S.), and JP17H05157 (M.N.), as well as by the Program for Leading Graduate Schools “Integrative Graduate Education and Research in Green Natural Sciences” from MEXT. T.Y. expresses his gratitude for a JSPS Research Fellowship for Young Scientists (JP16J10315). H.S. gratefully acknowledges the Murata Science Foundation for financial support. Work at the Yonsei University was supported by the Global Research Laboratory (2013K1A1A2A02050183) funded by the Ministry of Science, ICT and Future Planning.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201712961

Cite this

Yoshida, T., Takahashi, K., Ide, Y., Kishi, R., Fujiyoshi, J. Y., Lee, S., Hiraoka, Y., Kim, D., Nakano, M., Ikeue, T., Yamada, H., & Shinokubo, H. (2018). Benzonorcorrole Ni^II Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion. Angewandte Chemie - International Edition, 57(8), 2209-2213. https://doi.org/10.1002/anie.201712961

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title = "Benzonorcorrole NiII Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion",

abstract = "Fused benzene rings to antiaromatic compounds generally improve their stability but attenuate their antiaromaticity. The opposite case is now reported. NiII benzonorcorroles were synthesized and the effect of benzo-fusion on the antiaromaticity was elucidated. The benzo-fusion resulted in significant decrease of the HOMO–LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, the introduction of the benzo groups induced singlet diradical character in the antiaromatic porphyrinoid.",

author = "Takuya Yoshida and Kohtaro Takahashi and Yuki Ide and Ryohei Kishi and Fujiyoshi, {Jun Ya} and Sangsu Lee and Yuya Hiraoka and Dongho Kim and Masayoshi Nakano and Takahisa Ikeue and Hiroko Yamada and Hiroshi Shinokubo",

note = "Funding Information: This work was supported by JSPS KAKENHI grants JP26102003 (H.S.), JP15K21721 (H.S.), and JP17H05157 (M.N.), as well as by the Program for Leading Graduate Schools “Integrative Graduate Education and Research in Green Natural Sciences” from MEXT. T.Y. expresses his gratitude for a JSPS Research Fellowship for Young Scientists (JP16J10315). H.S. gratefully acknowledges the Murata Science Foundation for financial support. Work at the Yonsei University was supported by the Global Research Laboratory (2013K1A1A2A02050183) funded by the Ministry of Science, ICT and Future Planning. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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Yoshida, T, Takahashi, K, Ide, Y, Kishi, R, Fujiyoshi, JY, Lee, S, Hiraoka, Y, Kim, D, Nakano, M, Ikeue, T, Yamada, H & Shinokubo, H 2018, 'Benzonorcorrole Ni^II Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion', Angewandte Chemie - International Edition, vol. 57, no. 8, pp. 2209-2213. https://doi.org/10.1002/anie.201712961

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AU - Ide, Yuki

AU - Kishi, Ryohei

AU - Fujiyoshi, Jun Ya

AU - Lee, Sangsu

AU - Hiraoka, Yuya

AU - Kim, Dongho

AU - Nakano, Masayoshi

AU - Ikeue, Takahisa

AU - Yamada, Hiroko

AU - Shinokubo, Hiroshi

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