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Hirel C, Li L, Brough P, et al. New spin-transition-like copper(II)-nitroxide species. Inorg Chem. 2007;46(18):7545-52doi: 10.1021/ic700851x.
Hirel, C., Li, L., Brough, P., Vostrikova, K., Pécaut, J., Mehdaoui, B., Bernard, M., Turek, P., & Rey, P. (2007). New spin-transition-like copper(II)-nitroxide species. Inorganic chemistry, 46(18), 7545-52. https://doi.org/10.1021/ic700851x
Hirel, Catherine, et al. "New spin-transition-like copper(II)-nitroxide species." Inorganic chemistry vol. 46,18 (2007): 7545-52. doi: https://doi.org/10.1021/ic700851x
Hirel C, Li L, Brough P, Vostrikova K, Pécaut J, Mehdaoui B, Bernard M, Turek P, Rey P. New spin-transition-like copper(II)-nitroxide species. Inorg Chem. 2007 Sep 03;46(18):7545-52. doi: 10.1021/ic700851x. Epub 2007 Aug 02. PMID: 17672449.
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Inorg Chem. 2007 Sep 03;46(18):7545-52. doi: 10.1021/ic700851x. Epub 2007 Aug 02.

New spin-transition-like copper(II)-nitroxide species.

Inorganic chemistry

Catherine Hirel, Licun Li, Peter Brough, Kira Vostrikova, Jacques Pécaut, Boubker Mehdaoui, Maxime Bernard, Philippe Turek, Paul Rey

Affiliations

  1. CEA-Grenoble, Département de Recherche Fondamentale sur la Matière Condensée, Service de Chimie Inorganique et Biologique (UMR-E3, CEA-UJF), 17 rue des Martyrs F38054 Grenoble Cedex 09, France.

PMID: 17672449 DOI: 10.1021/ic700851x

Abstract

Novel copper(II)-nitroxide complexes exhibiting a spin-transition-like behavior have been prepared and characterized. They include meso, chiral, and racemic 2-(3-pyridyl)-nitronyl nitroxides differently substituted in positions 4 and/or 5 by ethyl groups and pyrimidyl nitroxides. Depending on the stoichiometry of the reaction, tetranuclear and binuclear complexes were obtained whose structures are cyclic. The tetranuclear species, which include two intracyclic and two exocyclic metal sites, are similar to the previously reported complex of the tetramethylated analogue, while the binuclear complexes involve only endocyclic metal ions and have uncoordinated N-oxyl groups. The tetranuclear complexes exist as two isomers depending on the temperature of crystallization: at room temperature, N-oxyl ligand coordination is axial-axial, while it is axial-equatorial at low temperature. Unexpectedly, this isomerism concerns N-oxyl bonding to the exocyclic metal centers for the derivatives of 4,5-diethyl-substituted ligands while it involves the endocyclic metal site in the complex of the monoethylated ligand, which converts reversibly from a high-spin state to a low-spin state, as observed for the complex of the tetramethylated ligand. Binuclear complexes are diamagnetic at room temperature but convert to a paramagnetic state on warming (90-110 degrees C); the transition is irreversible and sharp.

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