Perchlorophenalenyl radical
Date
2001Author

Chen, Y. Z.
Cao, Yun Zhen
Best, T. P.
Itkis, M. E.
Beer, L.
Oakley, R. T.
Cordes, A. W.
Brock, C. P.
Haddon, R. C.
Source
Journal of the American Chemical SocietyVolume
123Issue
17Pages
3864-3871Google Scholar check
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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 I 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.