TEMPO radicals showing magnetic interactions. I. 4-(4-Halobenzylideneamino)TEMPO and related compounds.
X-ray crystal structure analyses of the 4-(4-halobenzylideneamino)TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidyl-1-oxyl) radicals 4-(4-fluorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, 4-(4-chlorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, 4-(4-bromobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl and 4-(4-iodobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, and other 4-Ar-CH=N-TEMPO [Ar = 4-Ph-Ph, 2,2,6,6-tetramethyl-4-(4-phenylbenzylideneamino)piperidyl-1-oxyl, 4-Py, 2,2,6,6-tetramethyl-4-(4-pyridylmethylideneamino)piperidyl-1-oxyl, and 3,5-diCl-Ph, 4-(3,5-dichlorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl] radicals have been performed at room temperature. Some of these radicals show intermolecular ferromagnetic interactions at extremely low temperatures. X-ray analysis revealed that crystals of the 4-I-Ph derivative showed two modifications [(a) and (b)]; measurements of the magnetic properties of these crystals showed a ferromagnetic transition at an extremely low temperature for modification (a) and an antiferromagnetic interaction for modification (b). The structural features of these TEMPO radical crystals can be classified into three groups: (i) the crystal structures of the 4-Cl-Ph, 4-I-Ph(a) and 4-Ph-Ph derivatives, which show a ferromagnetic transition; (ii) the structures of the 4-Br-Ph and 4-Py derivatives, which show a ferromagnetic interaction (straight theta > 0); (iii) miscellaneous: the antiferromagnetic 4-F-Ph and 4-I-Ph(b) derivatives (straight theta < 0) and the ferromagnetic 3,5-diCl-Ph (straight theta > 0) derivative. Sheet-like arrangements of O atoms and intra-sheet interactions through the CH(2) or CH(3) groups of the TEMPO rings are related to the mechanisms of the ferromagnetic interactions.
Department of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan. fuji@pc.uec.ac.jp
F
Iwasaki
JH
Yoshikawa
H
Yamamoto
E
Kan-Nari
K
Takada
M
Yasui
T
Ishida
T
Nogami