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Pure Appl. Chem., 2008, Vol. 80, No. 3, pp. 507-517

Oxophenalenoxyl: Novel stable neutral radicals with a unique spin-delocalized nature depending on topological symmetries and redox states

Yasushi Morita1,2, Shinsuke Nishida3, Junya Kawai1, Takeji Takui3 and Kazuhiro Nakasuji1

1 Department of Chemistry, Osaka University, Toyonaka, Osaka 560-0043, Japan
2 PRESTO, Japan Science and Technology Agency, Honcho, Kawaguchi, Saitama 332-0012, Japan
3 Departments of Chemistry and Materials Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan

Abstract: Stable organic open-shell systems have attracted much attention in the field of molecule-based magnetism. We have been exploring novel stable neutral radicals based on a phenalenyl system known as an odd-alternant hydrocarbon π-radical with a highly spin-delocalized nature. Recently, we have designed and synthesized novel oxophenalenoxyl neutral radical systems possessing two oxygen atoms on the phenalenyl skeleton. These systems are unique in comprising some topological isomers depending on the positions of oxygen substituents on the phenalenyl skeleton. The isomers exhibit different topological symmetries of spin density distributions (spin topological symmetry control). In addition, two-stage one-electron reductions of these systems give the corresponding radical dianions, which show remarkably different topological symmetries of a spin-delocalized nature from those of the neutral radical systems (redox-based spin diversity). In this paper, we discuss the unique spin-delocalized nature of 3-, 4-, and 6-oxophenalenoxyl systems in view of the topological symmetry and redox ability, emphasizing the results from the radical dianion of 4-oxophenalenoxyl system from both experimental and theoretical sides.