Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene-within-an-Annulene Models

Hirokazu Miyoshi; Ryosuke Sugiura; Ryohei Kishi; Sarah N Spisak; Zheng Wei; Atsuya Muranaka; Masanobu Uchiyama; Nagao Kobayashi; Shreyam Chatterjee; Yutaka Ie; Ichiro Hisaki; Marina A Petrukhina; Tohru Nishinaga; Masayoshi Nakano; Yoshito Tobe

doi:10.1002/anie.202115316

Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene-within-an-Annulene Models

Angew Chem Int Ed Engl. 2022 Feb 1;61(6):e202115316. doi: 10.1002/anie.202115316. Epub 2021 Dec 23.

Authors

Hirokazu Miyoshi¹, Ryosuke Sugiura², Ryohei Kishi^{2

3}, Sarah N Spisak⁴, Zheng Wei⁴, Atsuya Muranaka⁵, Masanobu Uchiyama^{5

6}, Nagao Kobayashi⁷, Shreyam Chatterjee⁸, Yutaka Ie⁸, Ichiro Hisaki^{9

10}, Marina A Petrukhina⁴, Tohru Nishinaga¹¹, Masayoshi Nakano^{2

3

12

13

14}, Yoshito Tobe^{1

8

15}

Affiliations

¹ Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
² Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
³ Center for Quantum Information and Quantum Biology (QIQB), Osaka University, Toyonaka, Osaka, 560-8531, Japan.
⁴ Department of Chemistry, University of Albany, State University of New York, Albany, NY 12222, USA.
⁵ Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory RIKEN, 2-1 Hirosawa, Wako-shi, Saitama, 351-0198, Japan.
⁶ Graduate School of Pharmaceutical Sciences, The Universiy of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
⁷ Faculty of Textile Science and Technology, Shinshu University, Ueda, 386-8567, Japan.
⁸ Nanoscience and Nanotechnology Center, The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Ibaraki, Osaka, 567-0047, Japan.
⁹ Division of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
¹⁰ Research Institute for Electronic Science (RIES), Hokkaido University, Sapporo, Hokkaido, 001-0020, Japan.
¹¹ Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo, 192-0397, Japan.
¹² Center for Spintronics Research Network (CSRN), Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
¹³ Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka, 565-0871, Japan.
¹⁴ Research Center for Solar Energy Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
¹⁵ Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu, 30030, Taiwan.

PMID: 34873811
DOI: 10.1002/anie.202115316

Abstract

The dianion and dication of tetramesityl-substituted tetracyclopentatetraphenylene, a circulene consisting of alternating five- and six-membered rings, have been generated by reduction with alkali metals and oxidation with antimony(V) halides, respectively. They are theoretically predicted to adopt double annulenoid structures called annulene-within-an-annulene models in which the outer and inner conjugation circuits are significantly decoupled. The theoretical structures were experimentally proven by X-ray crystallographic analyses and the electronic configurations were supported by MCD spectra. Based on the ¹³ C NMR chemical shifts, negative and positive charges are shown to be located mainly at the outer periphery, indicating that the dianion and dication have delocalized 22-π and 18-π electron outer perimeters, respectively, and 8-π electron structure at the inner ring. Notably, the dianion has an open-shell character, whereas the dication has a closed-shell ground state.

Keywords: Annulenes; Circulenes; Dianion; Dication; Tropicity.

Abstract

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