Secondary-Sphere Chlorolanthanide(III) Complexes with a 1,3,5-Triazine-Based Ligand Supported by Anion-π, π-π, and...

2,4,6-Dipicolylamine-functionalized 1,3,5-triazine (dpat) was isolated. When reacted with LaCl₃, compound [(LaCl₆)(H₃dpat)][H₂O]₂ (1) formed, which crystallized in the monoclinic P2₁/n space group with parameters a = 11.47 Å, b = 19.22 Å, c = 20.98 Å, V = 4652.02 Å, and β = 90.53°. When reacted with NdCl₃, the complex [NdCl₃(H₂O)₄(H₃dpat)][Cl]₃(MeOH)₂ (2) crystallized in the monoclinic P2₁/n space group with unit cell parameters a = 20.05 Å, b = 12.81 Å, c = 20.64 Å, V = 5004.40 Å, and β = 110.20°. In both cases, the dpat ligand forms a bowl-shaped cavity that partially envelops the Ln^III-containing central unit, which is anionic in 1 and neutral in 2. The formation of these outer-sphere complexes is supported by secondary interactions, including π-π stacking, hydrogen bonding, and anion-π 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 [H₂dpat][Cl]₂ (3). This compound crystallized in the monoclinic C2/c space group with parameters a = 11.93 Å, b = 20.22 Å, c = 15.28 Å, V = 3664.97 Å, and β = 94.35°. Four pyridine rings are pairwise protonated in 3. dpat showed a moderate ability to extract La^III 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.