Two- and Three-Dimensional Lanthanide Complexes: Synthesis, Crystal Structures, and Properties

3,5-Pyrazoledicarboxylic acid (H3L) reacts with nitrate salts of lanthanide(III) (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, and Er) under hydrothermal conditions to form a series of lanthanide polymers 1−9. These nine polymers have
the same crystal system of monoclinic, but they exhibit three different kinds of metal−organic framework structures.
The complexes {[Ln2(HL)3(H2O)4]·2H2O}n (Ln = Pr (1), Nd (2), and Sm (3)) were isostructural and exhibited
porous 3D frameworks with a Cc space group. The complexes {[Ln2(HL)3(H2O)3]·3H2O}n (Ln = Eu (4), Gd (5),
and Tb (6)) were isostructural and built 2D double-decker (2DD) frameworks with a P21/c space group. The complexes
{[Ln(HL)(H2L)(H2O)2]}n ((Ln = Dy (7), Ho (8), and Er (9)) were also isostructural and formed 2D monolayer (2DM)
frameworks with a P21/n space group. The structure variation from the 3D porous framework to the 2D double-decker to the 2D monolayer is attributed to the lanthanide contraction effect. Notably, six new coordination modes
of 3,5-pyrazoledicarboxylic acid were observed, which proved that 3,5-pyrazoledicarboxylic acid may be used as
an effective bridging ligand to assemble lanthanide-based coordination polymers. The photophysical and magnetic
properties have also been investigated.