Perchlorophenalenyl radical

Citation
Pa. Koutentis et al., Perchlorophenalenyl radical, J AM CHEM S, 123(17), 2001, pp. 3864-3871
Citations number
38
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
0002-7863 → ACNP
Volume
123
Issue
17
Year of publication
2001
Pages
3864 - 3871
Database
ISI
SICI code
0002-7863(20010502)123:17<3864:PR>2.0.ZU;2-B
Abstract
We report the preparation and solid-state characterization of the perchloro phenalenyl radical (1). The radical is initially obtained as a yellow-green solid by reduction of the perchlorophenalenium salt (12(+)). This solid su blimes in a sealed tube to give black shiny hexagonal crystals of the perch lorophenaIenyl radical (1). The structure consists of I-dimensional stacks of the monomeric radical. The peri-chlorine atoms force the phenalenyl syst em to be strongly nonplanar leading to a large separation between adjacent molecules within the stacks (3.78 Angstrom), and the molecules adopt two di stinct stacking motifs (quasisuperimposed and rotated-by 60 degrees with re spect to neighbors). Because of the packing frustration in the lattice and the large intermolecular spacing, the solid shows Curie paramagnetism in th e temperature range 100-400 K, before antiferromagnetic coupling sets in at low temperatures. Due to the narrow bandwidth that results from the isolat ion of the individual molecules, the solid is a Mott-Hubbard insulator, wit h a room-temperature conductivity of rho (RT) = 10(-10) S/cm.