Manganese (II) coordination complexes involving nitronyl nitroxide radicals

Mohammed Fettouhi*, Mazen Khaled, Abdel Waheed, Stéphane Golhen, Lahcène Ouahab, Jean Pascal Sutler, Olivier Kahn

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

75 Scopus citations

Abstract

Three-new complexes involving nitronyl nitroxide and PhCOO- or N3- ligands have been synthesized and structurally and magnetically characterized. These compounds are formulated as Mn(L)4(X)2.nH2O, L = 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide(PNN)or 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-l-oxyl (PN) and X = PhCOO- or N3-. Compound A [Mn(PNN)2(PhCOO)2(H2O)2] presents the following structural parameters: triclinic, space group P1∼ (No. 2), a = 6.859(1) Å, b = 11.271(2) Å, c = 13.978(6) Å, α = 88.88(2)°, β -89.38(2)°, γ = 78.28(2)°, Z = 1. The complex has a centrosymmetric distorted octahedral geometry in which the manganese ion is bound to two radical ligands through the nitrogen atom of the pyridine rings, two benzoate groups, and two water molecules. The two compounds B [Mn(PNN)4(N3)2] and C [Mn(PN)4(N3)2] are isostructural with the following structural parameters: B; triclinic, space group P1∼ (No. 2), a = 7.177(4) Å, b = 13.767(3) Å, c = 13.928(4) Å, α = 90.20(2)°, β= 102.94(4)°, γ = 91.86(4)°, Z = 1; C, triclinic, space group P1∼ (No. 2), a = 7.004(2) Å, b = 13.885(1) Å, c = 14.036(2) Å, α = 90.34(1)°, β= 101.42(2)°, γ = 92.92(1)°, Z = l. They adopt a centrosymmetric tetragonally distorted octahedral geometry in which the manganese ion is bound to four radical ligands through the nitrogen atom of the pyridine rings, and the azido groups occupy the apical positions. For all three compounds A, B, and C intramolecular ferromagnetic interactions between the Mn(II) ion and the nitronyl nitroxide radicals are observed, but at very low temperatures, intermolecular antiferromagnetic interactions dominate.

Original languageEnglish
Pages (from-to)3967-3971
Number of pages5
JournalInorganic Chemistry
Volume38
Issue number18
DOIs
StatePublished - 1999

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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