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Article

Perchlorophenalenyl Radical

Supporting Info

P. A. Koutentis,^† Y. Chen,^† Y. Cao,^† T. P. Best,^† M. E. Itkis,^†^‡ L. Beer,^§ R. T. Oakley,^§ A. W. Cordes, C. P. Brock,^† and R. C. Haddon*^†^‡

Contribution from the Departments of Chemistry and Physics and Advanced Carbon Materials Center, University of Kentucky, Lexington, Kentucky 40506-0055, Departments of Chemistry and Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, and Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada

J. Am. Chem. Soc., 2001, 123 (17), pp 3864–3871

DOI: 10.1021/ja0018015

Publication Date (Web): April 10, 2001

†

University of Kentucky.

‡

Present address: Departments of Chemistry and Chemical & Environmental Engineering, University of California, Riverside, California 92521-0403.

University of Waterloo.

University of Arkansas.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

We report the preparation and solid-state characterization of the perchlorophenalenyl radical (1). The radical is initially obtained as a yellow-green solid by reduction of the perchlorophenalenium salt (12⁺). This solid sublimes in a sealed tube to give black shiny hexagonal crystals of the perchlorophenalenyl radical (1). The structure consists of 1-dimensional stacks of the monomeric radical. The peri-chlorine atoms force the phenalenyl system to be strongly nonplanar leading to a large separation between adjacent molecules within the stacks (3.78 Å), and the molecules adopt two distinct stacking motifs (quasisuperimposed and rotated by 60° with respect to neighbors). Because of the packing frustration in the lattice and the large intermolecular spacing, the solid shows Curie paramagnetism in the temperature range 100−400 K, before antiferromagnetic coupling sets in at low temperatures. Due to the narrow bandwidth that results from the isolation of the individual molecules, the solid is a Mott−Hubbard insulator, with a room-temperature conductivity of ρ_RT = 10^-¹⁰ S/cm.

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