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Synthesis of Three‐Dimensional Butterfly Slit‐Cyclobisazaanthracenes and Hydrazinobisanthenes through One‐Step Cyclodimerization and Their Properties
Author(s) -
Yamamoto Koji,
Higashibayashi Shuhei
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.201504144
Subject(s) - molecule , chemistry , conjugated system , butterfly , photochemistry , crystallography , organic chemistry , polymer , finance , economics
New three‐dimensional (3D) π‐conjugated molecules, butterfly‐shaped slit‐cyclobisazaanthracenes, were synthesized in high yields by Ni‐mediated one‐step cyclodimerization of dibromoazaanthracenes with a dimethylacridine, phenothiazine, or acridone skeleton. The 3D slit butterfly shape was formed by folded azaanthracene skeletons. Closure of the slit via NN bond formation afforded hydrazinobisanthenes with an embedded hydrazine structure in a bisanthene skeleton, which exhibited a 3D butterfly or a 2D plane structure depending on the type of heterocycle used. Extensive study of the stereoselective chemical reactivity of the butterfly shape, X‐ray analysis, DFT calculations, electrochemical/chemical oxidations, and photophysical measurements revealed that the properties of these materials included stereoselective oxidation, a rigid or flexible butterfly shape, dynamic conformational behavior, unique crystal‐packing structures, excellent electron donation with low oxidation potential, a radical cation, a long absorption wavelength, and fluorescence property.