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5,12‐Diaminotetracenes: The Impact of Orbital Interactions between the Acene π System and Amino Groups on Their Electronic States
Author(s) -
Uebe Masashi,
Kawashima Kenji,
Ito Akihiro
Publication year - 2018
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.201803090
Subject(s) - tetracene , moiety , acene , chemistry , planarity testing , molecular orbital , stereochemistry , atomic orbital , crystallography , photochemistry , anthracene , molecule , electron , organic chemistry , physics , quantum mechanics
Abstract 5,12‐Diamino‐substituted tetracenes with various N‐substituents have been prepared, and their molecular structural changes upon oxidation have been evaluated in association with their electronic structures. The N‐substituents influence both the electronic and molecular structures of the oxidized species of 5,12‐diaminotetracenes. The tetracene moiety of 5,12‐bis( N , N ‐dianisylamino)tetracene retained its planarity during the course of two successive one‐electron oxidations, whereas 5,12‐bis( N , N ‐dimethylamino)tetracene and 5,12‐bis( N ‐anisyl‐ N ‐methylamino)tetracene underwent substantial structural changes into butterfly like structures through a simultaneous two‐electron oxidation process. The molecular structures in the oxidized states were closely related to the nature of the highest occupied orbitals, which were characterized by the extent of mixing between the fragment orbitals for the teracene moiety and the substituted amino groups in 5,12‐diaminotetracenes. As a consequence, the present work revealed that the extent of folding deformation of the acene moiety in the oxidized diaminoacenes could be fine‐tuned by varying the N‐substituents.