Synthesis, X-ray structure, and solution NMR studies of Ln(III) complexes with a macrocyclic asymmetric compartmental Schiff base. Preference of the Ln(III) ions for a crown-like coordination site

The compartmental ligand H(2)L(A), containing an N(3)O(2) Schiff base and an O(2)O(3) crown like coordination site, has been prepared by reaction of 3,3'-(3-oxapentane-1,5-diyldioxy)bis(2-hydroxybenzaldehyde) with 1,5-diamino-3-azamethylpentane. The formation of a [1+1] macrocycle was inferred by IR, NMR, and mass spectrometry. When reacted with the rare-earth hydrate chlorides, LnCl(3). nH(2)O (Ln = La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y), H(2)L(A) or its precursors (template reaction) form the mononuclear complexes [Ln(H(2)L(A))(H(2)O)(4)]Cl(3). nH(2)O where the lanthanide ion coordinates the O(2)O(3) crown like site. The solid-state X-ray structures of [Ln(H(2)L(A))(H(2)O)(4)]Cl3 . nH2O (Ln = Ce, Dy, Lu) have been determined. [Lu(H(2)L(A))(H(2)O)(4)]Cl(3). 3H(2)O is monoclinic space group P2(1)/n (Z = 4) with a = 15.269(5) Angstrom, b = 11.484(5) Angstrom, c = 19.389(6) Angstrom, beta = 102.85(5)degrees; [Ce(H(2)L(A))(H(2)O)(4)]Cl(3). H(2)O and [Dy(H(2)L(A))(H(2)O)(4)]Cl(3). H(2)O are isomorphous, space group P2(1) (Z = 2), with a 10.959(5) Angstrom, b = 16.978(5) Angstrom, c = 9.017(4) Angstrom, beta = 97.73(5)degrees, and a = 10.874(5) Angstrom, b = 16.797(5) Angstrom, c = 9.046(4) Angstrom, beta = 97.86(5)degrees for the cerium and dysprosium complexes, respectively. In the three compounds the metal ion is coordinated in a similar manner by the five oxygens (two phenolic and three etheric) of the cyclic ligand and the nine coordination around the central atom is reached by the oxygen atoms of four coordinated water molecules. Three chlorine ions are present in the asymmetric unit. A detailed (1)H NMR study was carried out in CD(3)OD for both the diamagnetic and paramagnetic [Ln(H(2)L(A))(H(2)O)(4)]Cl(3) complexes in order to compare their structure in solution with that found in the solid state. The quantitative analysis of the paramagnetic proton shifts indicates that the complexes from La to Tm are isostructural, maintain in solution the same type of coordination polyhedron found at the solid state, with the metal ion invariably coordinated in the O(2)O(3) compartment, and present a high degree of stereochemical nonrigidity. In the case of the Lu complex, the decreased fluxionality due to the reduced ionic radius allows the observation of two isomeric species in the (1)H NMR spectrum at low temperature.