Resonating Valence Bond Ground State in Oxygen-Functionalized Phenalenyl-Based Neutral Radical Molecular Conductors

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• 作者：Swadhin K. Mandal ; Satyabrata Samanta ; Mikhail E. Itkis ; Dell W. Jensen ; Robert W. Reed ; Richard T. Oakley ; Fook S. Tham ; Bruno Donnadieu ; and Robert C. Haddon
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：February 15, 2006
• 年：2006
• 卷：128
• 期：6
• 页码：1982 - 1994
• 全文大小：466K
• 年卷期：v.128,no.6(February 15, 2006)
• ISSN：1520-5126

文摘

We report the preparation, crystallization, and solid-state characterization of the first two membersof a new family of spiro-bis(1,9-disubstituted phenalenyl)boron neutral radicals based solely on oxygenfunctionalization, and we show that this strategy significantly lowers the electrochemical disproportionationpotentials (E), in comparison with other spiro-bis(1,9-disubstituted phenalenyl)boron salts. In the solidstate, these radicals pack in a continuous array of --stacked phenalenyl units with very shortintermolecular carbon···carbon contacts. These two radicals are among the most highly conducting neutralorganic solids, with room temperature conductivities reaching 0.3 S/cm. Magnetic susceptibility measurements show that the radicals do not exist as isolated free radicals, and there is significant spin-spininteraction between the molecules in the solid state as expected from the crystal structures and the calculatedband structures; the solid-state properties are best rationalized in terms of the resonating valence bondmodel.