Effect of the lanthanoid-size on the structure of a series of lanthanoid-anilato 2-D lattices

Abstract

We report the synthesis and characterization of a series of Ln-based bromoanilato 2-D lattices with dimethyl sulfoxide (DMSO): [Ln2(C6O4Br2)3(DMSO)n]·2DMSO·mH2O with n = 6 and m = 0 for Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6) and Gd (7); n = 4 and m = 2 for Ln = Tb (8), Dy (9), Ho (10), Er (11), Tm (12) and Yb (13) (C6O4Br22− = 3,6-dibromo-2,5-dihydroxy-1,4-benzoquinone = bromoanilato). The X-ray analysis shows that the largest Ln(III) ions (La-Gd, 1-7) crystallize in the monoclinic P21/n space group (phase I), whereas the smaller Ln(III) ions (Tb–Yb, 8–13) crystallize in the triclinic P-1 space group (phase II). Both phases present a (6,3)-2-D topology but show important differences derived from the different coordination number of the Ln(III) in both phases. In phase I, the Ln(III) ions are nine-coordinate with a tri-capped trigonal prism geometry and rectangular cavities with no solvent molecules. In phase II, the Ln(III) ions are eight-coordinate with a triangular dodecahedral geometry and distorted hexagonal cavities having two water molecules. These differences are due to the lanthanoid contraction. The magnetic properties show that the Ln(III) ions are isolated and do not present any noticeable magnetic interactions as expected for bromoanilato bridges and Ln(III) ions.