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Complexes of the Lighter Lanthanoid Nitrates with 15-crown-5 and 18-crown-6 ethers: Synthesis and characterization

✍ Scribed by Jean-Claude G. Bünzli; Denis Wessner

Publisher
John Wiley and Sons
Year
1978
Tongue
German
Weight
462 KB
Volume
61
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Complexes of lanthanoid trinitrates Ln(NO~3~)~3~ with 15‐crown‐5 ether 1 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) and with 18‐crown‐6 ether 2 (Ln = La, Ce, Pr, Nd) having a 1:1 stoichiometry as well as 4:3 complexes with 2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) have been synthesized and characterized. All the isolated complexes are solvent free. At 170–220° the 1:1 complexes of 2 are quantitatively transformed into 4:3 complexes. X‐Ray powder diagrams of the neodymium complexes with 2 indicate that both the 1:1 and 4:3 complexes are genuine compounds. All the 1:1 complexes show a characteristic IR. absorption band at 875–880 cm^−1^ absent from both the spectra of the free ligands and of the 4:3 complexes.

The spectroscopic properties (IR. and electronic spectra, fluorescence lifetimes) of the complexes and the low magnetic moments of the Ln(III) ions in the complexes with Ln = Ce‐Eu are indicative of a strong interaction between the lanthanoid ions and the crown ethers 1 and 2.

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