Are Inorganic Single-Molecule Magnets a Possibility? A Theoretical Insight into Dysprosium Double-Deckers with
Kamil Kotrle1, Radovan Herchel1
1Department of Inorganic Chemistry, Faculty of Science , Palacký University Olomouc , 17. listopadu 12 , 771 46 Olomouc , Czech Republic.
Abstract:
Computational studies of sandwich dysprosium double-decker complexes [Dy(L)2]+/3+ as candidates for single-ion magnets with several inorganic aromatic ring systems (P5-, N5-, B3N3H6, B3P3H6, B3S3H3) have been performed. The molecular structures were optimized with the TPSSh functional, and the ground state properties were investigated with the complete active space SCF method (CASSCF) complemented by the dynamic correlation dressed correction (DCD-CAS(2)) or NEVPT2. Besides the evaluation of the magnetic moment blocking barrier, the impact of the molecular vibration on the relaxation of magnetization was also inspected. We were able to make predictions about the performance of those molecules as single-molecule magnets, where estimated effective energy barrier, Ueff, values are as high as 1475 K in the case of [Dy(N5)2]-, which is the most anisotropic complex from our choice of studied compounds, making them a potentially very effective carbon-free alternative to organometallic double-decker dysprosocenium high-temperature single-molecule magnets.
More Related Videos
Related Concept Videos
02:42Valence Bond Theory
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...
02:46Crystal 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,...
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....
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...