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

Mandal, Swadhin K. ; Samanta, Satyabrata ; Itkis, Mikhail E. ; Jensen, Dell W. ; Reed, Robert W. ; Oakley, Richard T. ; Tham, Fook S. ; Donnadieu, Bruno ; Haddon, Robert C. (2006) Resonating Valence Bond Ground State in Oxygen-Functionalized Phenalenyl-Based Neutral Radical Molecular Conductors Journal of the American Chemical Society, 128 (6). pp. 1982-1994. ISSN 0002-7863

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Official URL: http://doi.org/10.1021/ja0560276

Related URL: http://dx.doi.org/10.1021/ja0560276

Abstract

We report the preparation, crystallization, and solid-state characterization of the first two members of a new family of spiro-bis(1,9-disubstituted phenalenyl)boron neutral radicals based solely on oxygen functionalization, and we show that this strategy significantly lowers the electrochemical disproportionation potentials (ΔE), in comparison with other spiro-bis(1,9-disubstituted phenalenyl)boron salts. In the solid state, these radicals pack in a continuous array of π−π-stacked phenalenyl units with very short intermolecular carbon···carbon contacts. These two radicals are among the most highly conducting neutral organic 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−spin interaction between the molecules in the solid state as expected from the crystal structures and the calculated band structures; the solid-state properties are best rationalized in terms of the resonating valence bond model.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:118392
Deposited On:20 May 2021 18:05
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