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Bis‐Copper(II)/π‐Radical Multi‐Heterospin System with Non‐innocent Doubly N ‐Confused Dioxohexaphyrin(1.1.1.1.1.0) Ligand
Author(s) -
Yamasumi Kazuhisa,
Nishimura Keiichi,
Hisamune Yutaka,
Nagae Yusuke,
Uchiyama Tomoki,
Kamitani Kazutaka,
Hirai Tomoyasu,
Nishibori Maiko,
Mori Shigeki,
Karasawa Satoru,
Kato Tatsuhisa,
Furukawa Ko,
Ishida Masatoshi,
Furuta Hiroyuki
Publication year - 2017
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.201704321
Subject(s) - unpaired electron , delocalized electron , antiaromaticity , chemistry , electron paramagnetic resonance , copper , radical , ligand (biochemistry) , crystallography , paramagnetism , divalent , redox , open shell , photochemistry , bridging ligand , aromaticity , inorganic chemistry , crystal structure , molecule , nuclear magnetic resonance , organic chemistry , physics , receptor , quantum mechanics , biochemistry
A contracted doubly N ‐confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open‐shell π‐radical ligand was synthesized as a new multi‐heterospin motif. X‐ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the presence of unpaired d electrons strongly antiferromagnetically coupled with π‐radicals delocalized on the macrocycle. The 25 π non‐innocent dioxohexaphyrin ligand allowed the facile interconversion between antiaromatic 24 π and aromatic 26 π species, respectively, upon redox reactions.