Asymmetric Assembly of Chiral Lanthanide(III) Tetranuclear Cluster Complexes Using Achiral Mixed Ligands:
Cai-Ming Liu1,2, Xiang Hao1
1Beijing National Laboratory for Molecular Sciences, Center for Molecular Science, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Abstract:
It is challenging to use achiral ligands to spontaneously construct chiral molecular magnets. In this work, two new Ln4 cluster complexes based on N,N'-(1,3-propanediyl)bis[N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]amine] (H6L) have been assembled, which are crystallized in a chiral space group due to the asymmetric distribution of acetate (OAc-) groups and hexafluoroacetylacetonate (F6acac-) groups on both sides of the parallelogram-like Ln4 core. Complex 1, [Dy4(H3L)2(OAc)3(F6acac)3]·5MeOH·2H2O, exhibits single-molecule magnet properties at the zero field with the U eff/k value of 48.4 K; notably, besides the Orbach process, the Raman process is also prominent for the magnetic relaxation of 1. Complex 2, [Gd4(H3L)2(OAc)3(F6acac)3]·4MeOH·2.5H2O, displays a large magnetocaloric effect, whose largest -ΔS m value is 21.88 J kg-1 K-1 (when T = 2 K and ΔH = 5 T); it thus can be utilized as a good magnetic refrigeration molecular material.
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...
01:19Complexation Equilibria: The Chelate Effect
02:52Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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...
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,...