Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México, D.F. 04510, México.
Inorg Chem. 2010 May 3;49(9):4109-16. doi: 10.1021/ic902120e.
New lanthanide complexes with 4,5-bis(diphenyl)phosphoranyl-1,2,3-triazolate (L(-)), LnL(3).nH(2)O (1-8) and LnL(3)(phen).nH(2)O (9-16) (Ln = La, Ce, Nd, Sm, Eu, Gd, Tb, Er), have been prepared and spectroscopically characterized. The structures of LnL(3).nH(2)O (Ln = La, Ce, Nd, Sm and Gd) were determined by X-ray crystallography. The metal centers exhibit a distorted trigonal dodecahedron coordination environment with two symmetrically O,O-bidentate ligands and one unsymmetrically O,N- ligand attached to the metal; two oxygen atoms from neighboring dimethyl sulfoxide (DMSO) molecules complete the coordination sphere. This unsymmetrical ligand coordination behavior was also identified in solution through (31)P{(1)H} NMR studies. Photoluminescence spectroscopy experiments in CH(2)Cl(2) for both types of complexes containing Eu(III) (6, 14) and Tb(III) (7, 15) exhibit strong characteristic red and green emission bands for Eu(III) and Tb(III), respectively. Furthermore, NdL(3) (phen).5H (2)O (11) displays emission in the near-infrared spectral region ((4)F(3/2) --> (4)F(9/2) at 872 nm and (4)F(3/2) --> (4)F(11/2) at 1073 nm). The complexes containing 1,10-phenantroline exhibit higher quantum yields upon excitation at 267 nm, indicating that this auxiliary ligand promotes the luminescence of the complexes; however, luminescence lifetimes (tau) in this case are shorter than those of the LnL(3).nH(2)O series.
已制备并光谱表征了具有 4,5-双（二苯基）膦酸-1,2,3-三唑（L(-)）、LnL(3).nH(2)O（1-8）和 LnL(3)(phen).nH(2)O（9-16）（Ln = La、Ce、Nd、Sm、Eu、Gd、Tb、Er）的新型镧系元素配合物。通过 X 射线晶体学确定了 LnL(3).nH(2)O（Ln = La、Ce、Nd、Sm 和 Gd）的结构。金属中心呈现出扭曲的三角十二面体配位环境，两个对称的 O,O-双齿配体和一个不对称的 O,N-配体连接到金属上；来自相邻二甲亚砜（DMSO）分子的两个氧原子完成配位球。通过（31）P{(1)H}NMR 研究也在溶液中鉴定了这种不对称配体配位行为。CH(2)Cl(2)中两种类型的配合物（Eu(III)（6、14）和 Tb(III)（7、15））的光致发光光谱实验分别显示出 Eu(III)和 Tb(III)的强特征红光和绿光发射带。此外，NdL(3)(phen).5H(2)O（11）在近红外光谱区（872nm 处的（4）F(3/2) --> (4)F(9/2)和 1073nm 处的（4）F(3/2) --> (4)F(11/2)）显示出发射。含有 1,10-菲啰啉的配合物在 267nm 激发时表现出更高的量子产率，表明该辅助配体促进了配合物的发光；然而，在这种情况下，发光寿命（tau）比 LnL(3).nH(2)O 系列短。
