Magnetic and ⁵⁷Fe Mössbauer Study of the Single Molecule Magnet Behavior of a Dy₃Fe₇ Coordination Cluster
The reaction between N-methydiethanolamine (mdeaH2), benzoic acid, FeCl3, and DyCl3 yields a decanuclear coordination cluster, [Dy3Fe7(µ4-O) 2(µ3-OH)2(mdea)7(µ-benzoate) 4(N3)6] · 2H2O · 7CH3OH (1) whose single crystal structure exhibits three and seven crystallog raphically distinct Dy(III) and Fe(III) Ions; six of the Fe(III) Ions arepseudo octahedrally coordinated, whereas the seventh has a trigonal-bipyramldal coordination geometry. Both direct current (dc) and alternating current (ac) magnetic susceptibility studies Indicate that, upon cooling, intracluster antlferromagnetlc interactions are dominant In 1, yielding a ferrlmagnetic spin arrangement. The out-of-phase (X") ac susceptibility reveals that 1 undergoes a slow relaxation of its magnetization mainly resulting from the anlsotropy of the Dy(III) Ions. This slow relaxation has been confirmed both by magnetization measurements on an oriented single crystal of 1 and by the observation of hysteresis loops below 1.9 K. The macroscopic magnetic studies yield an effective energy barrier, Ueff, of 33.4 K for this relaxation, a barrier that is the highest yet reported for a lanthanlde(III)Fe(III) single molecule magnet. The 57Fe Mössbauer spectra of 1 obtained between 3 and 35 K are consistent with the presence of Fe(III) intracluster antiferromagnetic coupling with slow magnetic relaxation relative to the Larmor precession time, thus confirming, on a microscopic scale, the presence of a barrier to the magnetic relaxation below 35 K. Between 55 and 295 K the Mössbauer spectra reveal paramagnetic behavior with six partially resolved quadrupole doublets, one for the trigonal-bipyramidal Fe(III) site and five for the six pseudo-octahedral Fe(III) sites.
G. Abbas and Y. Lan and V. M. Mereacre and W. Wernsdorfer and R. Clérac and G. Buth and M. T. Sougrati and F. Grandjean and G. J. Long and C. E. Anson and A. K. Powell, "Magnetic and ⁵⁷Fe Mössbauer Study of the Single Molecule Magnet Behavior of a Dy₃Fe₇ Coordination Cluster," Inorganic Chemistry, vol. 48, no. 19, pp. 9345-9355, American Chemical Society (ACS), Aug 2009.
The definitive version is available at https://doi.org/10.1021/ic901248r
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© 2009 American Chemical Society (ACS), All rights reserved.
01 Aug 2009