Nucleophile Assistance of Electron-Transfer Reactions between Nitrogen Dioxide and Chlorine Dioxide Concurrent with the Nitrogen Dioxide Disproportionation

A series of tris(2-pyridylmethyl)amines including one and two asymmetric centers were synthesized in a stereocontrolled fashion as potential ligands of lanthanide cations. The reaction of chiral pyridylethyl methanesulfonates and bis(pyridylmethyl)amines occurred via an SN2 mechanism with complete inversion of asymmetric centers and gave the stereocontrolled tris(2-pyridylmethyl)amines, the stereochemical purity of which was ascertained by GPC, NMR, X-ray, and polarimetry experiments. They formed stable Tb^3 and Eu^3 complexes having 1:1, 1:2, and 1:3 stoichiometry (metal:ligand) in CH3CN solutions. NMR and UV titration experiments revealed that their complexation behaviors were rarely influenced by ligand chirality but significantly affected by the nature of the counteranion and the concentration ratio of metal to ligand. The Tb^3 and Eu^3+ complexes with these tripodal ligands exhibited characteristic luminescence spectra upon excitation for pyridine chromophores (260 nm), the intensities of which were largely dependent on the ligand chirality. The meso isomer of the disubstituted tripods particularly exhibited the enhanced terbium luminescence ca. three times more than its diastereomer and un- and monosubstituted tripods. Direct excitation at the lanthanide center had similar chirality effects on the luminescence profiles, indicating that the stereochemistry of the employed ligand largely influenced the lanthanide emitting processes. Since the ligand chirality finely modified the local coordination environments around the lanthanide center, the use of stereocontrolled ligands is applicable in design of the luminescent lanthanide complexes.