Trinuclear to dinuclear: a radii dependence lanthanide(III) self-assembly coordination behavior of an amide-type tripodal ligand

Lanthanide nitrate complexes with the heptadentate ligand L (6-2-(2-(diethylamino)-2-oxoethoxy)ethyl]-N,N,12-triethyl-11-oxo-3,9-dioxa-6,12-diazatetradecanamide), Ln(2)L(NO(3))(6)] (Ln = La, Nd, Sm, Eu, Ho), have been prepared and characterized. The X-ray crystallographic studies show that, in La(2)L(NO(3))(6)(H(2)O)].H(2)O (1), two complex cations LaL(H(2)O)](3+) are linked by a hexanitrato anion La(NO(3))(6)](3)(-) and form a trinuclear cation. In Nd(2)L(NO(3))(6)(H(2)O)].CHCl(3).1/2CH(3)OH.1/2H(2)O (2), one complex cation NdL(H(2)O)](3+) and a hexanitrato complex anion Nd(NO(3))(6)](3)(-) are linked by a bridging NO(3)(-) to form a dinuclear complex. In both complexes, the bridging nitrate is an unusual tetradentate ligand. The metal ions are 12-coordinated in hexanitrato anions and 10-coordinated in complex cations. The chainlike supramolecular structures of La(3+) complex are parallel and have no hydrogen bonds in between, while, in the Nd(3+) complex, a chiral cavity is formed by hydrogen bonds between two adjacent supramolecular chains. These influences are further investigated by assessing the separation efficiency of L and (1)H NMR spectra of its lanthanide nitrate mixtures in solution.