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. 2021 Jun 14;60(25):13877-13881.
doi: 10.1002/anie.202103667. Epub 2021 May 10.

Synthesis and Characterization of 16π Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen

Takumi Nakazato  1 , Haruka Takekoshi  1 , Takahiro Sakurai  1 , Hiroshi Shinokubo  1 , Yoshihiro Miyake  1
Affiliations

Synthesis and Characterization of 16π Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen

Takumi Nakazato et al. Angew Chem Int Ed Engl. .

Abstract

We describe the two-electron reduction of N,N'-dimethyl-2,7-diazapyrenium dications (MDAP2+ ), which afforded the corresponding reduced form (MDAP0 ) as a highly electron-rich 16π antiaromatic system. A single-crystal X-ray diffraction analysis of MDAP0 revealed a distorted quinoidal structure with high bond-length alternation. The 1 H NMR spectrum of MDAP0 exhibited a diagnostic proton signal (4.6 ppm) that is distinctly upfield shifted compared to that of aromatic diazapyrene (8.3 ppm). Theoretical calculations supported the existence of a paratropic ring current. These results indicate that MDAP0 exhibits antiaromatic character derived from its peripheral 16π-electron conjugation.

Keywords: 2,7-diazapyrene; antiaromaticity; electron-rich; reduction.

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