Related Experiment Video
Updated: Nov 9, 2025
Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
Published on: April 14, 2020
Spin Crossover and High-Spin State in Fe(II) Anionic Polymorphs Based on Tripodal Ligands
Emmelyne Cuza1, Cle Donacier Mekuimemba1, Nathalie Cosquer1
1Univ Brest, CNRS, CEMCA, 6 Avenue Le Gorgeu, C.S. 93837-29238 Brest Cedex 3, France.
Abstract:
Two new mononuclear Fe(II) polymorphs, [(C2H5)4N]2[Fe(py3C-OEt)(NCS)3]2 (1) and [(C2H5)4N][Fe(py3C-OEt)(NCS)3] (2) (py3C-OEt = tris(pyridin-2-yl)ethoxymethane), have been synthesized and characterized by single-crystal X-ray diffraction, by magnetic and photomagnetic measurements, and by detailed variable-temperature infrared spectroscopy. The molecular structure, in both complexes, is composed of the same anionic [Fe(py3C-OEt)(NCS)3]- complex (two units for 1 and one unit for 2) generated by coordination to the Fe(II) metal center of one tridentate py3C-OEt tripodal ligand and three terminal κN-SCN coligands. Magnetic studies revealed that polymorph 2 displays a high-spin (HS) state over the entire studied temperature range (300-10 K), while complex 1 exhibits an abrupt and complete spin crossover (SCO) transition at ca. 132.3 K, the structural characterizations of which, performed at 295 and 100 K, show a strong modification, resulting from the thermal evolutions of the Fe-N bond lengths and of the distortion parameters (∑ and Θ) of the FeN6 coordination sphere, in agreement with the presence of HS and low-spin (LS) states at 295 and 100 K, respectively. This thermal transition has been also confirmed by the thermal evolution of the maximum absorbance for ν(NCS) vibrational bands recorded in the temperature range 200-10 K. In 1 the signature of a metastable photoinduced HS state has been observed using photomagnetic and photoinfrared spectroscopy, leading to a similar T(LIESST) relaxation temperature (LIESST = light-induced excited spin-state trapping) of 70 K.
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...
02:58Crystal 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...
01:17Spin–Spin Coupling: One-Bond Coupling
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,...
01:03Atomic Nuclei: Nuclear Spin State Overview