Crystal structures and luminescence properties of [Eu(ODA)·(phen)·4H2O]+, [Tb(ODA)·(phen)·4H2O]+ and [Tb(ODA)3]3− (ODA: oxydiacetate, phen: 1,10-phenanthroline)

Two novel complexes of Eu(III) and Tb(III) with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and a Tb(III) complex with homoleptic ODA were prepared and their crystal structures were determined: [Eu(ODA)·(phen)·4H2O]Cl·5H2O, monoclinic, P21/n, a = 12.3197(12) Å, b = 16.7992(17) Å, c = 12.6754(10) Å, β = 107.981(8)°, V = 2495.2(4) Å3, Z = 4, R(|F|) = 0.0324 for 5728 data; [Tb(ODA)·(phen)·4H2O]Cl·5H2O monoclinic, P21/n, a = 12.2846(13) Å, b = 16.7560(14) Å, c = 12.6681(11) Å, β = 108.144(8)°, V = 2478.0(4) Å3, Z = 4, R(|F|) = 0.0279 for 4364 data; Na3[Tb(ODA)3]·8H2O monoclinic, Cc, a = 15.751(3) Å, b = 9.8030(14) Å, c = 18.189(4) Å, β = 105.513(15)°, V = 2706.2(9) Å3, Z = 4, R(|F|) = 0.0406 for 3435 data. In these structures, the rare earth ions satisfy nine-coordination via binding to tridentate ODA, bidentate phen or water molecules. The geometry of the nine-coordinate polyhedron is discussed in terms of the dihedral angle and the mean plane. uminescence (PL) and excitation spectra of Eu(III) and Tb(III) complexes with mixed ODA and phen ligands and with homoleptic ODA are reported. The complexes of [Eu(ODA)·(phen)·4H2O]+ and [Tb(ODA)·(phen)·4H2O]+ excited by UV light produce very bright red and green emissions, respectively, via the nonradiative energy-transfer from phen to the metals. For [Eu(ODA)·(phen)·4H2O]+ and [Tb(ODA)·(phen)·4H2O]+, the quantum yields of the sensitized luminescence (Q = 6.6 and Q = 75.7%, respectively) are much greater than those of the nonsensitized luminescence (Q = 2.0 and Q = 21.0%, respectively).