A Water-Soluble Pybox Derivative and Its Highly Luminescent Lanthanide Ion Complexes

摘要

A new water-soluble Pybox ligand, 1, has been synthesized and found to crystallize in the monodinic P2_1 space group with unit cell parameters a = 6.0936(1) A, b - 20.5265(4) A, c = 12.0548(2) A, and β = 90.614(1)°. In the crystal, a water molecule is bound through hydrogen-bonding interactions to the nitrogen atoms of the oxazoline rings. This ligand was used to complex a variety of lanthanide ions, opening up new avenues for luminescence and catalysis in aqueous environment. These complexes are highly luminescent in aqueous solutions, in acetonitrile, and in the solid state. Aqueous quantum yields are high at 30.4% for Eu(Ⅲ), 26.496 for Tb(Ⅲ), 0.32% for Yb(Ⅲ), and 0.11% for Nd(Ⅲ). Er(Ⅲ) did not luminesce in water, but an emission efficiency of 0.20% could be measured in D_2O. Aqueous emission lifetimes were also determined for the visible emitting lanthanide ions and are 1.61 ms for Eu(Ⅲ) and 1.78 ms for Tb(Ⅲ). Comparing emission lifetimes in deuterated and nondeuterated water indicates that no water molecules are coordinated to the metal ion. Speciation studies show that three species form successively in solution and the log P values are 5.3, 9.6, and 13.8 for Eu(Ⅲ) and 5.3, 9.2, and 12.7 for Tb(Ⅲ) for 1:1, 2:1, and 3:1 ligand to metal ratios, respectively.