Lanthanide(III) complexes have been prepared with [L1]- [the tetradentate chelating ligand bis{3-(2-pyridyl)pyrazolyl}dihydroborate], [L2]- [the tetradentate chelating ligand bis{3-(2-pyrazinyl)pyrazolyl}dihydroborate], [L3]- [the hexadentate chelating ligand bis[3-{6‘-(2,2‘-bipyridyl)}pyrazol-1-yl]dihydroborate], and [L4]2- [the 12-dentate compartmental ligand hexakis{3-(2-pyridyl)pyrazol-1-yl}diboran(IV)ate, which has two hexadentate tris(pyrazolyl)borate-based cavities linked “back-to-back” by a B−B bond]. [Ln(L1)2(NO)3] are 10-coordinate with two tetradentate N-donor ligands and one bidentate nitrate. [Ln(L2)2(NO)3] have 10-coordinate structures similar to those of the [L1]- complexes except that the coordinated N1 of the pyrazine rings is not such a good donor as the pyridine rings in the [L1]- complexes, leading to marked lengthening of these Ln−N bonds. [Ln(L3)(NO3)2] are also 10-coordinate from one hexadentate chelating ligand which has a pseudoequatorial coordination mode and two pseudoaxial bide...