期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 6, 期 5, 页码 1188-1196出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.201000793
关键词
density functional calculations; EPR spectroscopy; radicals; resonance structures; valence-bond methods
资金
- Yazaki Memorial Foundation for Science and Technology
- Japan Securities Scholarship Foundation
- Kansai Research Foundation for technology promotion
- Ministry of Education, Culture, Sports, Science and Technology, Japan
- Core Research for Evolutional Science and Technology (CREST-JST)
- FIRST project on Quantum Information Processing
- [20110006]
- Grants-in-Aid for Scientific Research [23655041, 22350018] Funding Source: KAKEN
A new 2,5-di-tert-butyl-6-oxophenalenoxyl (6OPO) derivative with a cyano group at the 8-position, where a large spin density resides, has been synthesized. This neutral radical exhibits high stability in the solid state in air despite the low steric protection on the 8-position; the stability is comparable to that of a corresponding 8-tert-butylated 6OPO derivative. EPR/(HENDOR)-H-1/TRIPLE (electron paramagnetic resonance/H-1-electron-nuclear double resonance/TRIPLE) spectroscopy and cyclic voltammetry showed an extended spin delocalization on the cyano group and a significant increase in electron-accepting ability relative to that of the 8-tert-butylated 6OPO derivative. DFT calculations indicated the extension of a singly occupied molecular orbital (SOMO) onto the cyano group and the lower-lying SOMO and LUMO in comparison with those of the 8-tert-butylated 6OPO derivative, which was consistent with experimental results. Furthermore, the extended nature of p conjugation onto the cyano group was quantitatively evaluated by calculating the contributing weights of resonance structures in terms of a molecular orbital (MO)-based valence-bond (VB) method. Herein, the synthesis and physical properties of the 8-cyano-6OPO derivative are described, emphasizing that the high stability arises from the electronic effect of the cyano group. Also, the usefulness of the quantitative resonance structure analysis is shown.
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