Para-Derivatized Pybox Ligands As Sensitizers in Highly Luminescent Ln(III) Complexes

New complexes of pyridine-bis(oxazoline) derivatized with -H, -OMe, and -Br at the para position of the pyridine ring with Eu(III) and Tb(III) have been isolated. These are highly luminescent in the solid state, regardless of the ligand-to-metal ratio. Several of the metal complexes were isolated and characterized by single crystal X-ray diffraction, showing the rich diversity of structures that can be obtained with this family of ligands. [Eu(PyboxOMe)(3)](NO(3))(3)center dot 3CH(2)Cl(2), 1, crystallizes in the monoclinic space group P2(1)/n and has the cell parameters a = 14.3699(10) angstrom, b = 13.4059(9) angstrom, c = 25.8766(18) angstrom, beta = 95.367(1), and V = 4963,1(6) angstrom(3). The isostructural [Tb(PyboxOMe)(3)](NO(3))(3)center dot 3CH(2)Cl(2), 2, crystallizes with the parameters a = 14.4845(16) angstrom, b = 13.2998(15) angstrom, c= 25.890(3) angstrom, beta = 94.918(2)degrees, and V= 4969.1(10) angstrom(3). 3, a 1:1 complex.with the formula [Eu(PyboxBr)(NO(3))(3)(H(2)O)], crystallizes in the monoclinic P2(1)/c space group with a= 11.649(2) angstrom, b = 8.3914(17) angstrom, c= 20.320(4) angstrom, beta = 100.25(3)degrees, and V= 1954.5(7) angstrom(3). 4, a product of the reaction of PyboxBr with Tb(NO(3))(3), is [Tb(PyboxBr)(2)(eta(2)-NO(3))(eta(1)-NO(3)](2)[Tb(NO(3))(5)]center dot 5H(2)O. It crystallizes in the monoclinic space group P2(1) with a = 15.612(3) angstrom, b= 14.330(3) angstrom, c= 16.271(3) angstrom, beta = 92.58(3)degrees, and V= 3636.5(13) angstrom(3). [Tb(Pybox)(3)](CF(3)SO(3))(3). 3CH(2)CN, 5, crystallizes in the triclinic space group P (1) over bar with a =12.3478(2)angstrom, b = 15.0017(2) angstrom, c= 16.1476(4) angstrom, alpha = 100.252(1)degrees, beta = 100.943(1)degrees, gamma = 113.049(1)degrees, and V= 2594.80(8) angstrom(3). Finally, compound 6, [Tb(Pybox)(2)(NO(3))(H(2)O)](NO(3))(2).CH(3)OH, crystallizes in the triclinic P (1) over bar space group with a = 9.7791(2) angstrom, b= 10.1722(2) angstrom, c= 15.3368(3) angstrom, alpha= 83.753(1)degrees, beta =78.307(1)degrees, gamma =85.630(1)degrees, and V= 1482.33(5) angstrom(3). In solution, the existence of 3:1, 2:1, and 1:1 species can be observed through absorption and luminescence speciation measurements as well as NMR spectroscopy. The stability constants in acetonitrile, as an average obtained from absorption and emission titrations, are log beta(11) = 5.4, log beta(12) = 8.8, and log beta(13) = 12.8 with Eu(III) and log beta(11) = 4.5, log beta(12) = 8.4, and log beta(13) = 11.7 for the Tb(III) species with PyboxOMe. Pybox displayed stability constants log beta(11) = 3.6, log beta(12) = 9.1, and loci beta(13) = 12.0 with Eu(III) and log beta(11) = 3.7, log beta(12) = 9.3, and log beta(13) = 12.2 for the Tb(III) species. Finally, PyboxBr yielded log beta(11) = 7.1, log beta(12) = 12.2, and log beta(13) = 15.5 for the Eu(III) species and log beta(11) = 6.2, log beta(12) = 11.0, and log beta(13) = 15.4 with Tb(III). Photophysical characterization was performed in all cases on solutions with 3:1 ligand-to-metal io stoichiometry and allowed determination of quantum yields and lifetimes of emission for PyboxOMe of 23.5 +/- 1.6% and 1.54 +/- 0.04 ms for Eu(III) and 21.4 +/- 3.6% and 1.88 +/- 0.04 ms for Tb(III). For Pybox these values were 25.6 +/- 1.1% and 1.49 +/- 0.04 ms for Eu(III) and 23.2 +/- 2.1% and 0.44 +/- 0.01 ms for Tb(III) and for PyboxBr they were 35.8 +/- 1.6% and 1.46 +/- 0.03 ms for Eu(III) and 23.3 +/- 1.3% and a double lifetime of 0.79 +/- 0.05/0.07 +/- 0.01 ms for Tb(III). angstrom linear relationship between the triplet level energies and the Hammett a constants was found. Lifetime measurements in methanol as well as the NMR data in both methanol and acetonitrile indicate that all complexes are stable in the 3:1 stoichiometry in solution and that there is no solvent coordination to the metal ion.