Premium
9,10‐Diaminoanthracenes Revisited: The Influence of N ‐Substituents on Their Electronic States
Author(s) -
Uebe Masashi,
Kato Tatsuhisa,
Tanaka Kazuyoshi,
Ito Akihiro
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602490
Subject(s) - anthracene , moiety , molecular orbital , chemistry , planarity testing , amine gas treating , atomic orbital , crystallography , stereochemistry , molecule , electron , photochemistry , organic chemistry , physics , quantum mechanics
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.