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
Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395, Japan.
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 819-0395, Japan.
Chemistry. 2017 Nov 2;23(61):15322-15326. doi: 10.1002/chem.201704321. Epub 2017 Oct 11.
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.
一种由两个顺磁性铜金属和开壳层π-自由基配体组成的缩合双N-稠合二氧代六卟啉（1.1.1.1.1.0）配合物被合成为一种新的多异自旋基序。X射线光谱证实了内部铜中心的二价性质，电子顺磁共振和磁学研究表明存在未成对的d电子，其与大环上离域的π-自由基强烈反铁磁耦合。25π非无害二氧代六卟啉配体在氧化还原反应中分别允许反芳香性24π和芳香性26π物种之间的轻松相互转化。
