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Journal of Thermal Analysis and Calorimetry
Authors:
W. Ferenc
,
A. Dziewulska-Kułaczkowska
,
J. Sarzyński
, and
B. Paszkowska

Abstract  

4-Chloro-2-methoxybenzoates of heavy lanthanides(III) and yttrium(III) were obtained as mono-, di-, tri-or tetrahydrates with metal to ligand ratio of 1:3 and general formula Ln(C8H6ClO3)3·nH2O, where n=1 for Ln=Er, n=2 for Ln=Tb, Dy, Tm, Y, n=3 for Ln=Ho and n=4 for Yb and Lu. The complexes were characterized by elemental analysis, FTIR spectra, TG, DTA and DSC curves, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical bidentate chelating ligand. All complexes are polycrystalline compounds. The values of enthalpy, ΔH, of the dehydration process for analysed complexes were also determined. The solubilities of heavy lanthanide(III) 4-chloro-2-methoxybenzoates in water at 293 K are of the order of 10−4 mol dm−3. The magnetic moments were determined over the range of 76–303 K. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature.

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Abstract  

4-Chloro-2-methoxybenzoates of light lanthanides(III) were obtained as mono-, di-or trihydrates with metal to ligand ratio of 1:3 and general formula Ln(C8H6ClO3)3·nH2O, where n=1 for Ln=Ce, Pr, n=2 for Ln=Nd, Sm, Eu, Gd and n=3 for Ln=La. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric studies, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical bidentate, chelating ligand. All complexes seem polycrystalline compounds. Their thermal stabilities were determined in air. When heated they dehydrate to form anhydrous salts which next are decomposed to the oxides of the respective metals. The solubilities of light lanthanide(III) 4-chloro-2-methoxybenzoates in water at 293 K are of the order of 10−5 mol dm−3. The magnetic moments were determined over the range of 77–300 K. They obey the Curie-Weiss law. The values of μeff calculated for all compounds are close to those obtained for Ln3+ by Hund and Van Vleck. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature.

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