title: Modification of calix[4]arenes with CMPO-functions at the wide rim. Synthesis, solution behavior, and separation of actinides from lanthanides.
abstract: Two calix[4]arene tetraethers (Y = C5H11, C14H29) bearing on their wide rim four -N(Me)-CO-CH2-P(O)Ph2 residues were synthesized for the first time. Their ability to extract lanthanides and actinides from an acidic aqueous phase to organic phases (CH2Cl2, NPHE) was studied. In comparison to the corresponding -NH-analogs, they are less efficient extractants, the selectivity for the light over the heavy lanthanides is less pronounced, while there is still an interesting selectivity of Am3+ over Eu3+. Stability constants for selected lanthanide salts were determined also in homogenous phase (methanol, acetonitrile) but do not account for the different extraction results. The complexation of Gd3+ was also followed by relaxivity (NM RD) measurements, which suggest an even stronger aggregation for the N-methyl compound while the 1:1 complex is reached for a smaller ratio [L]/[Gd3+] compared to the NH analog. The formation of aggregates is also supported by dynamic light scattering measurements. A single crystal X-ray structure of the pentyl ether reveals a C2-symmetrical pinched cone conformation for the free ligand.
authors.affiliation: Fachbereich Chemie und Pharmazie, Abteilung Lehramt Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, D-55099 Mainz, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Schmidt
authors.forename: Mohamed
authors.initials: M
authors.lastname: Saadioui
authors.forename: Volker
authors.initials: V
authors.lastname: Böhmer
authors.forename: Valéry
authors.initials: V
authors.lastname: Host
authors.forename: Marie-Rose
authors.initials: MR
authors.lastname: Spirlet
authors.forename: Jean F
authors.initials: JF
authors.lastname: Desreux
authors.forename: Fréderic
authors.initials: F
authors.lastname: Brisach
authors.forename: Françoise
authors.initials: F
authors.lastname: Arnaud-Neu
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Dozol