Ferromagnetic Exchange and Slow Magnetic Relaxation in Cobalt Bis(1,2-dithiolene)-Bridged Dilanthanide Complexes
Alexandre H Vincent1, Daphné Lubert-Perquel2,3, Stephen Hill2,4,5
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Abstract:
The construction of multinuclear lanthanide-based molecules with significant magnetic exchange interactions represents a key challenge in the realization of single-molecule magnets with high operating temperatures. Here, we report the synthesis and magnetic characterization of two series of heterobimetallic compounds, (Cp*2Ln)2(μ-Co(pdt)2) (Ln = Y3+, Gd3+, Dy3+; pdt2 = 1,2-diphenylethylenedithiolate) and [K(18-crown-6)][(Cp*2Ln)2(μ-Co(pdt)2)] (Ln = Y3+, Gd3+), featuring two lanthanide centers bridged by a cobalt bis(1,2-dithiolene) complex. Dc magnetic susceptibility data collected for the Gd congeners indicate significant Gd-Co ferromagnetic exchange interactions with fits affording J = +11.5 and +7.33 cm-1, respectively. Magnetization decay and ac magnetic susceptibility measurements carried out on the single-molecule magnet (Cp*2Dy)2(μ-Co(pdt)2) reveal full suppression of quantum tunneling and open-loop hysteresis persisting up to 3.5 K. These results, along with those of high-field EPR spectroscopy, suggest that transition metalloligands can enforce strong exchange interactions with adjacent lanthanide centers while maintaining a geometry that preserves molecular anisotropy. Furthermore, the magnetic properties of [K(18-crown-6)][(Cp*2Gd)2(μ-Co(pdt)2)] show that increasing the spin of the ground state of the bridging complex may be a viable alternative to increasing J in obtaining well-isolated, strongly coupled magnetic ground states.
More Related Videos
13:21Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
Published on: July 21, 2011
11:44Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
Published on: November 12, 2016
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:42Valence Bond Theory
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
01:26Diamagnetism
Diamagnetism was discovered by Anton Brugmans in 1778 when he observed that bismuth gets repelled by magnetic fields, thus theorizing that diamagnets get repelled by magnets....
01:31Ferromagnetism
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...