A Möbius Aromatic [28]Hexaphyrin Bearing a Diethylamine Group: A Rigid but Smooth Conjugation Circuit1. Issue 18 (4th February 2015)

• Record Type: Journal Article
• Authors: Higashino, Tomohiro; Soya, Takanori; Kim, Woojae; Kim, Dongho; Osuka, Atsuhiro
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 18(2015)
• Page Start: 5456
• Page End: 5459
• Publication Date: 2015-02-04
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201500099
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of [26]hexaphyrin with triethylamine in the presence of BF₃⋅OEt₂ and O₂ furnished a diastereomeric mixture of a diethylamine‐bearing [28]hexaphyrin as a rare example of a Möbius aromatic metal‐free expanded porphyrin. The Möbius aromaticity of these molecules is large, as indicated by their large diatropic ring currents, which are even preserved at 100 °C, owing to their internally multiply bridged robust structure with a smooth conjugation network. These molecules were reduced with NaBH₄ to give an antiaromatic [28]hexaphyrin, and were oxidized with MnO₂ to give aromatic [26]hexaphyrins, both through a Möbius‐to‐Hückel topology switch induced by a CN bond cleavage.</p> </abstract>