Perchlorophenalenyl radical
by Koutentis, P. A.; Chen, Y.; Cao, Y.; Best, T. P.; Itkis, M. E.; Beer, L.; Oakley, R. T.; Cordes, A. W.; Brock, C. P.; Haddon, R. C.
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 perchlorophenaIenyl radical (1). The structure consists of I-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 Angstrom), and the molecules adopt two distinct stacking motifs (quasisuperimposed and rotated-by 60 degrees 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 rho (RT) = 10(-10) S/cm.
- Journal
- Journal of the American Chemical Society
- Volume
- 123
- Issue
- 17
- Year
- 2001
- Start Page
- 3864-3871
- URL
- https://dx.doi.org/10.1021/ja0018015
- ISBN/ISSN
- 1520-5126; 0002-7863
- DOI
- 10.1021/ja0018015