9, 10‐Diaminoanthracenes Revisited: The Influence of N‐Substituents on Their Electronic States. Issue 52 (16th November 2016)

• Record Type: Journal Article
• Authors: Uebe, Masashi; Kato, Tatsuhisa; Tanaka, Kazuyoshi; Ito, Akihiro
• Is Part Of: Chemistry. Volume 22:Issue 52(2016)
• Page Start: 18923
• Page End: 18931
• Publication Date: 2016-11-16
• Subjects: acenes -- arylamines -- density functional calculations -- electrochemistry -- UV/Vis spectroscopy; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201602490
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The electronic and molecular structures of 9, 10‐diamino‐substituted anthracenes with different N ‐substituents have been re‐examined. In particular, different N ‐substituents influence both the electronic and molecular structures of the oxidized species of 9, 10‐diaminoanthracenes. The anthrylene moiety of 9, 10‐bis( N, N ‐di( p ‐anisyl)amino)anthracene retains its planarity during the course of two successive one‐electron oxidations, whereas 9, 10‐bis( N, N ‐dimethylamino)anthracene and 9, 10‐bis( N ‐ p ‐anisyl‐ N ‐methylamino)anthracene undergo a substantial structural change to a butterfly‐like structure through a two‐electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above‐mentioned three kinds of 9, 10‐diaminoanthracenes due to different extents of mixing between the amine‐localized and anthrylene‐localized orbitals. Abstract : Substituent effects on oxidation : 9, 10‐Diaminoanthracenes with N ‐substituents have been re‐examined. Substituent variation influences electronic and molecular structures of the oxidized species (see graphic). Structural changes observed for the oxidized states may be ascribed to significant differences in the frontier molecular orbitals of 9, 10‐diaminoanthracenes due to mixing of amine‐ and anthrylene‐localized orbitals.