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Perchlorophenalenyl Radical

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posted on 10.04.2001, 00:00 by P. A. Koutentis, Y. Chen, Y. Cao, T. P. Best, M. E. Itkis, L. Beer, R. T. Oakley, A. W. Cordes, C. P. Brock, R. C. Haddon
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 ρRT = 10-10 S/cm.