TEMPO radicals showing magnetic interactions. II. 4-(Benzylideneamino)-TEMPO and related compounds.
X-ray crystal structure analyses were performed on 4-(Ar-methyleneamino)-TEMPO radicals at room temperature (TEMPO = 2,2,6,6-tetramethylpiperidyl-1-oxyl): Ar = Ph [4-(benzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl], 4-MeS-Ph [2,2,6,6-tetramethyl-4-(4-methylthiobenzylideneamino)piperidyl-1-oxyl], 4-Me-Ph [4-(4-methylbenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl], 4-PhO-Ph [2,2,6,6-tetramethyl-4-(4-phenoxybenzylideneamino)piperidyl-1-oxyl], 4-MeSO(2)-Ph [2,2,6,6-tetramethyl-4-(4-methylsulfonylbenzylideneamino)piperidyl-1-oxyl], 3-Py [2,2,6,6-tetramethyl-4-(3-pyridylmethylideneamino)piperidyl-1-oxyl] and 2-Naph [2,2,6,6-tetramethyl-4-(2-naphthylideneamino)piperidyl-1-oxyl]. Structures of Ph and 4-Me-Ph derivatives were also determined at 100 K. Some of these crystals have been revealed to show intermolecular ferromagnetic interactions at an extremely low temperature. Structural features of crystals of Ph, 4-MeS-Ph and 3-Py derivatives, which show ferromagnetic interactions, are very similar to each other. In these crystals, O atoms are arranged to form a sheet. The ferromagnetic interactions are considered to be transferred through O.H van der Waals' interactions of the beta-H atoms of the neighboring TEMPO rings within the sheet. Between O.O sheets, the aryl groups are arranged in a herringbone manner. The crystal structure of the 4-Me-Ph derivative, which shows an antiferromagnetic interaction, is also pseudo-isostructural with those of Ph, 4-MeS-Ph and 3-Py derivatives, while the arrangement of the aryl groups is different. The packing mode of the crystals of the 4-MeSO(2)-Ph derivative, of which the Weiss constant straight theta is nearly zero, is very different from those of the other derivatives showing magnetic interactions. The fact that the crystal structure of the paramagnetic 4-MeSO(2)-Ph derivative does not show the O.O sheet structure accompanying the O.beta-H interactions indicates that the intermolecular ferromagnetic interactions through beta-H atoms within the O.O sheet are important for these TEMPO radical crystals.
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
K
Takada
E
Kan-Nari
M
Yasui
T
Ishida
T
Nogami