American Chemical Society
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Superoctazethrene: An Open-Shell Graphene-like Molecule Possessing Large Diradical Character but Still with Reasonable Stability

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journal contribution
posted on 2018-09-28, 00:00 authored by Wangdong Zeng, Tullimilli Y. Gopalakrishna, Hoa Phan, Takayuki Tanaka, Tun Seng Herng, Jun Ding, Atsuhiro Osuka, Jishan Wu
Laterally extended zethrenes can be regarded as Z-shaped nanographenes with four zigzag edges, but their synthesis is very challenging. Herein, we report the successful synthesis of by far the largest zethrene molecule, a superoctazethrene (SOZ) derivative SOZ-Cl, in crystalline form. Although the parent SOZ is calculated to have a very large diradical character (y0 = 81.0%), SOZ-Cl shows reasonable stability (t1/2 = 64 h under ambient conditions) and can be purified by silica gel column chromatography. It exhibits a small electrochemical energy gap (Eg = 1.01 eV) and characteristics for open-shell singlet diradicaloids. Compared with a previously reported octazethrene derivative (OZ-TIPS), SOZ-Cl shows much larger diradical character (y0 = 76.3% vs 43.4%) and smaller singlet–triplet gap (ΔES‑T = −2.30 kcal/mol vs −3.87 kcal/mol). Calculations also demonstrate global aromatic character of SOZ, but the smaller size octazethrene shows local aromaticity.