2,4,6-Dipicolylamine-functionalized 1,3,5-triazine (dpat) was isolated. When reacted with LaCl3, compound [(LaCl6)(H(3)dpat)][H2O](2) (1) formed, which crystallized in the monoclinic P2(1)/n space group with parameters a = 11.47 angstrom, b = 19.22 angstrom, c = 20.98 angstrom, V = 4652.02 angstrom, and beta = 90.53 degrees. When reacted with NdCl3, the complex [NdCl3(H2O)(4) (H(3)dpat)][Cl](3) (MeOH)(2) (2) crystallized in the monoclinic P2(1)/n space group with unit cell parameters a = 20.05 angstrom, b = 12.81 angstrom, c = 20.64 angstrom, V = 5004.40 angstrom, and beta = 110.20 degrees. In both cases, the dpat ligand forms a bowl-shaped cavity that partially envelops the Ln(III)-containing central unit, which is anion-pi in 1 and neutral in 2. The formation of these outer-sphere complexes is supported by secondary interactions, including pi-pi stacking, hydrogen bonding, and anion-pi between the chlorolanthanide(III) fragment and the electron-deficient 1,3,5-triazine ring. Evidence of protonation of the pyridine rings in dpat was substantiated through the isolation of [H(2)dpat] [Cl](2) (3). This compound crystallized in the monoclinic C2/c space group with parameters a = 11.93 angstrom, b = 20.22 angstrom, c = 15.28 angstrom, V = 3664.97 angstrom, and beta = 94.35 degrees. Four pyridine rings are pairwise protonated in 3. dpat showed a moderate ability to extract La m from an aqueous to an organic phase, indicating its potential, through judicious manipulation of secondary-sphere interactions, as the starting point for efficient extractants for Ln(III) ions.