Halogen Bond Mediated Self-Assembly of Mononuclear Lanthanide Complexes: Perception of Supramolecular Interactions,...

Five new mononuclear lanthanide complexes, [LnL₂][Et₃NH]·THF/H₂O (Ln = Nd, Tb, Dy) (H₂L^Cl = 2-bis(2-hydroxy-3,5-dichloro benzyl)aminomethyl]pyridine), Ln = Nd (1), Tb (2), and Dy (3), and (H₂L^Br = 2-bis(2-hydroxy-3,5-dibromo benzyl)aminomethyl]pyridine), Ln = Nd (4, H₂O) and Tb (5), were synthesized and structurally characterized by single-crystal X-ray diffraction analyses. Being isostructural in all the five cases, the metal center is octa-coordinated with a triangular dodecahedron (D₂ symmetry) geometry, and it is independent of the halogen substitution (Cl/Br). This close similarity is due to the composite interplay of hydrogen/halogen bond interactions that control the overall crystal packing, yet notable differences in association patterns among the individual ones arise from the subtle stereo-electronic requirement of individual molecules in the three-dimensional (3D) architecture. Hirshfeld surface and density functional theory (DFT) calculations clearly vouch for the importance of the hydrogen bond and halogen bond interactions observed in the structure. Detailed magnetic measurements using direct-current and alternating-current susceptibility measurements show slow magnetic relaxation in 3, a characteristic feature of the single-molecule magnets (SMMs), which is not shown by 1 and 2. Steady-state and time-resolved photoluminescence of Tb(III) complexes shows a strong ligand-to-metal energy transfer that can be modulated by changing the substitution on phenolic ligands. The results from these analyses indicate that it may be advantageous to consider the subtle role of hydrogen bond (HB)/halogen bond (XB) intermolecular interactions judiciously for the design of SMMs and luminescent materials based on halogen-substituted ligands.