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A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State
Author(s) -
Sakamaki Daisuke,
Yano Soichiro,
Kobashi Toshiyuki,
Seki Shu,
Kurahashi Takuya,
Matsubara Seijiro,
Ito Akihiro,
Tanaka Kazuyoshi
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201502949
Subject(s) - triphenylamine , homo/lumo , electronic structure , open shell , molecule , radical , resonance (particle physics) , crystallography , chemistry , derivative (finance) , atom (system on chip) , photochemistry , materials science , computational chemistry , atomic physics , physics , organic chemistry , computer science , financial economics , economics , embedded system
Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual CN bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.