Temperature dependence of the crystal lattice organization of coordination compounds involving nitronyl nitroxide radicals: a magnetic and structural investigation. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2002

Temperature dependence of the crystal lattice organization of coordination compounds involving nitronyl nitroxide radicals: a magnetic and structural investigation.

Résumé

Four new mononuclear complexes of formula Cd(PN)(4)(NCS)(2) (A), Cd(PNN)(4)(N(3))(2) (B), Zn(PNN)(4)(N(3))(2) (C), and Zn(PNN)(2)(NCS)(2) (D), where PNN stands for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and PN for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl, were synthesized and structurally and magnetically characterized. The X-ray structures of compounds B and C were also determined at 90 K. Compounds A[bond]C crystallize in the triclinic space group P 1 macro (No. 2), and D crystallizes in the monoclinic space group P2(1)/m (No. 11). A[bond]C adopt a centrosymmetric distorted octahedral geometry in which the metal ions are bonded to four radical ligands through the nitrogen atom of the pyridyl rings and the azido or thiocyanato ligands occupy the apical positions. Compound D adopts a distorted tetrahedral geometry in which the zinc ion is bonded to two radicals and two thiocyanato ligands. As suggested by their magnetic behavior, the low-temperature X-ray structures of B and C show that these compounds undergo a clear structural change with respect to the room-temperature structures. The experimental magnetic behaviors were perfectly reproduced by a dimer model for A[bond]C and an alternating chain model for D while the sudden breaks observed in the chi(M)T versus T curves for B and C were well accounted for by the high- and low-temperature X-ray structures. For all these complexes the crystal structures favor significant overlap between molecular magnetic orbitals leading to rather strong intermolecular antiferromagnetic interactions.

Domaines

Matériaux

Dates et versions

hal-00717025 , version 1 (11-07-2012)

Identifiants

Citer

Mohammed Fettouhi, Bassam El-Ali, Abdel Moneim El-Ghanam, Stéphane Golhen, Lahcène Ouahab, et al.. Temperature dependence of the crystal lattice organization of coordination compounds involving nitronyl nitroxide radicals: a magnetic and structural investigation.. Inorganic Chemistry, 2002, 41 (14), pp.3705-3712. ⟨10.1021/ic020021p⟩. ⟨hal-00717025⟩
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