Structure, magnetism, and theoretical study of a mixed-valence Co(II)3Co(III)4 heptanuclear wheel: lack of SMM behavior despite negative magnetic anisotropy

Journal of the American Chemical Society
Liviu F ChibotaruDominique Luneau

Abstract

A mixed-valence Co(II)/Co(III) heptanuclear wheel [Co(II)3Co(III)4(L)6(MeO)6] (LH2 = 1,1,1-trifluoro-7-hydroxy-4-methyl-5-aza-hept-3-en-2-one) has been synthesized and its crystal structure determined using single-crystal X-ray diffraction. The valence state of each cobalt ion was established by bond valence sum calculations. Studies of the temperature dependence of the magnetic susceptibility and the field dependence of the magnetization evidence ferromagnetic interactions within the compound. In order to understand the magnetic properties of this Co7 wheel, we performed ab initio calculations for each cobalt fragment at the CASSCF/CASPT2 level, including spin-orbit coupling effects within the SO-RASSI approach. The four Co(III) ions were found to be diamagnetic and to give a significant temperature-independent paramagnetic contribution to the susceptibility. The spin-orbit coupling on the three Co(II) sites leads to separations of approximately 200 cm(-1) between the ground and excited Kramers doublets, placing the Co7 wheel into a weak-exchange limit in which the lowest electronic states are adequately described by the anisotropic exchange interaction between the lowest Kramers doublets on Co(II) sites. Simulation of the exc...Continue Reading

Citations

Jun 4, 2011·Inorganic Chemistry·Rémi MauriceFrank Neese
Apr 24, 2012·Inorganic Chemistry·Asamanjoy BhuniaGereon Niedner-Schatteburg
Jun 6, 2012·Inorganic Chemistry·Sarah PetitDominique Luneau
May 23, 2013·Inorganic Chemistry·Liviu UngurLiviu F Chibotaru
Nov 19, 2013·Inorganic Chemistry·Daniel Aravena, Eliseo Ruiz
Mar 24, 2011·Journal of the American Chemical Society·Jérôme LongMuralee Murugesu
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Oct 27, 2011·Physical Chemistry Chemical Physics : PCCP·Liviu Ungur, Liviu F Chibotaru
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