1+1] Asymmetric Compartmental Macrocycles Bearing a Pendant Arm and Related s,f‐Heterodinuclear Complexes Containing Lanthanide(III) and Sodium Ions

Abstract

Abstract[1+1] Asymmetric compartmental macrocycles and/or related mononuclear, homodinuclear and sodium(I)‐lanthanide(III) heterodinuclear complexes are reported and their properties investigated by SEM‐EDS microscopy and 1H, 13C and 23Na NMR spectroscopy. These ligands bear a pendant arm, represented by a ‐CH2COOH (H3LA), ‐CH2C5H4N (H2LB) or‐CH2C6H4OH (H3LC) group bonded to the aminic nitrogen, and contain an O2O3 crown‐ether‐like chamber and an N3XO2 (where X = O, N) Schiff‐base chamber. It was found that the lanthanide(III) ion resides in the N3XO2 chamber while the sodium(I) ion fills the O2O3 crown‐ether‐like chamber, as ascertained for the complex [DyNa(LC)(PrOH)(Cl)] by a single‐crystal X‐ray structural investigation. The complex is monoclinic, space group P21/c, with a = 9.601(2), b = 12.927(2), c = 26.638(4) Å, β = 99.55(3)°. The dysprosium ion is seven‐coordinate in the N3O2 site, showing a pentagonal‐bipyramid‐coordination polyhedron and bonded, in the axial positions, to a chlorine ion and to the oxygen of the pendant phenolic group of the ligand. The sodium ion is six‐coordinate in the O3O2 site and bonded to the propyl alcohol oxygen. Furthermore, the potential use of these complexes as molecular probes for the selective recognition of specific metal ions has been tested. In particular, their ability to act as shift reagents towards Na+ was investigated by 23Na NMR spectroscopy. The relationship between the structure of these complexes in the solid state and in solution is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)