Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction. Issue 23 (7th April 2020)

• Record Type: Journal Article
• Authors: Han, Yi; Xue, Zibo; Li, Guangwu; Gu, Yanwei; Ni, Yong; Dong, Shaoqiang; Chi, Chunyan
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 23(2020)
• Page Start: 9026
• Page End: 9031
• Publication Date: 2020-04-07
• Subjects: azulenes -- nanostructures -- reaction mechanisms -- rearrangements -- Scholl reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201915327
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyloxylated product were obtained, as confirmed by X‐ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring‐fused substructure containing two formal azulene units is formed, but only one of them shows an azulene‐like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1, 2‐phenyl migration and a naphthalene to azulene rearrangement reaction according to an in‐silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene‐based molecular materials. Abstract : Shifting groups : An unprecedented naphthalene to azulene rearrangement reaction was observed during the Scholl reaction. And an arenium ion mediated 1, 2‐phenyl shift also took place. Combined these steps lead to azulene‐embedded nanographene structures having azulene‐like electronic and physical properties.