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An Estimation Method of Metal‐Ligand Orbital Mixing in Lanthanide(III) Complexes Using Magnetic Circular Dichroism
Author(s) -
Kitagawa Yuichi,
Nakanishi Takayuki,
Fushimi Koji,
Hasegawa Yasuchika
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201800050
Subject(s) - lanthanide , magnetic circular dichroism , chemistry , circular dichroism , mixing (physics) , crystallography , metal , ligand (biochemistry) , spectral line , electron configuration , transition metal , absorption spectroscopy , spin (aerodynamics) , ion , physics , catalysis , biochemistry , receptor , organic chemistry , quantum mechanics , astronomy , thermodynamics
The photophysical properties of lanthanide(III) complexes depend on the magnitude of orbital mixing between the lanthanide(III) and ligands. Herein, an estimation method of orbital mixing in lanthanide(III) complexes is reported using LnCl 3 ⋅ n H 2 O (Ln=Pr, Gd, Tb) and Ln(tfa) 3 (H 2 O) 2 (tfa: trifluoroacetylacetonate, Ln=Pr, Gd, and Tb) for the first time. The electronic state properties were assessed from the electronic absorption and magnetic circular dichroism (MCD) spectra. The MCD spectra revealed the energy levels of the spin‐allowed and spin‐forbidden 4 f–5d transitions of the Tb(III) complex that is hidden by the intense π–π* transition of the ligands. This energy gap corresponds to the exchange splitting energy between the 5d and 4f n−1 electrons, which provides information regarding the orbital mixing between the Tb(III) ion and the ligands.