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Hydroxyquinoline-Calix[4]arene-Conjugates as Ligands for Polynuclear Lanthanide Complexes: Preparation, Characterization, and Properties of a Dinuclear Eu(III) complex

Jäschke, A.; Kischel, M.; Mansel, A.; Kersting, B.


The synthesis of a calixarene-based N4O4 donor ligand H6L, in which two 8-hydroxyquinoline-2-carbaldehyde units are appended via hydrazone-carbonylmethoxy linkages in a 1,3-arrangement to the lower rim of tert-butyl-calix[4]arene, and its coordination properties towards Eu(III) are described. The reaction of H6L with Eu(NO3)3.6H2O produces a dinuclear complex [Eu2(H3L)2] (4). The Eu(III) ions in 4 are well-separated from each other (d > 8 Å) each being coordinated by two tetradentate hydroxyquinoline-2-carbaldehyde-hydrazone substituents from two triply deprotonated molecules (H3L)3- in a dodecahedral geometry. As a consequence there are no exchange interactions between the Eu(III) ions, and the magnetic properties are solely associated with thermal population of excited (7F1-7F6) terms. The spin-orbit coupling constant lambda is 325.2(4) cm-1. Moreover, the ligand H6L was found to extract Eu(III) and Tb(III) at pH 7-8 from aqueous solution, as established by radiotracing using the short-lived radionuclides 160Tb and 152Eu.

Keywords: Polynuclear Complex; 8-Hydroxyquinoline; Calix[4]arene; Europium; Extraction