期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 57, 期 14, 页码 3733-3736出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201801080
关键词
aminyl radicals; EPR; porphyrins; SQUID; stable high-spin radicals
资金
- JSPS KAKENHI Grant [25220802, 16K13952, 16J05512]
- JSPS
- Grants-in-Aid for Scientific Research [16J05512] Funding Source: KAKEN
A benzene-1,3,5-triaminyl radical fused with three Zn-II-porphyrins was synthesized through a three-fold oxidative fusion reaction of 1,3,5-tris(Zn-II-porphyrinylamino)benzene followed by oxidation with PbO2 as key steps. This triaminyl radical has been shown to possess a quartet ground state with a doublet-quartet energy gap of 3.1kJmol(-1) by superconducting quantum interference device (SQUID) studies. Despite its high-spin nature, this triradical is remarkably stable, which allows its separation and recrystallization under ambient conditions. Moreover, this triradical can be stored as a solid for more than one year without serious deterioration. The high stability of the triradical is attributed to effective spin delocalization over the porphyrin segments and steric protection at the nitrogen centers and the porphyrin meso positions.
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