Song Xueqin, Zhou Xiaoyan, Liu Weisheng, Dou Wei, Ma Jingxin, Tang Xiaoliang, Zheng Jiangrong
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China.
Inorg Chem. 2008 Dec 15;47(24):11501-13. doi: 10.1021/ic8008267.
To explore the relationships between the structures of ligands and their complexes, we have synthesized and characterized a series of lanthanide complexes with two structurally related ligands, 1,1,1,1-tetrakis{[(2'-(2-benzylaminoformyl))phenoxyl]methyl}methane (L(I)) and 1,1,1,1-tetrakis{[(2'-(2-picolyaminoformyl))phenoxyl]methyl}methane (L(II)). A series of zero- to three-dimensional lanthanide coordination complexes have been obtained by changing the substituents on the Pentaerythritol. Our results revealed that, complexes of the L(I) ligand, {Ln(4)L(I)(3)(NO(3))(12).nC(4)H(10)O}(infinity) (Ln = Nd, Eu, Tb, Er, n = 3 or 6)] show the binodal 3,4-connected three-dimensional interpenetration coordination polymers with topology of a (8(3))(4)(8(6))(3) notation. Compared to L(I), complexes of L(II) present a cage-like homodinuclear [Ln(2)L(II)(2)(NO(3))(6).2H(2)O].nH(2)O (Ln = Nd, Tb, Dy, n = 0 or 1) or a helical one-dimensional coordination {[ErL(II)(NO(3))(3).H(2)O].H(2)O}(infinity) polymer. The luminescence properties of the resulting complexes formed with ions used in fluoroimmunoassays (Ln = Eu, Tb) are also studied in detail. It is noteworthy that subtle variation of the terminal group from benzene to pyridine not only sensibly affects the overall molecular structures but also the luminescence properties as well.
为了探究配体及其配合物结构之间的关系,我们合成并表征了一系列镧系配合物,这些配合物由两种结构相关的配体构成,即1,1,1,1-四{[(2'-(2-苄基氨基甲酰基))苯氧基]甲基}甲烷(L(I))和1,1,1,1-四{[(2'-(2-吡啶基氨基甲酰基))苯氧基]甲基}甲烷(L(II))。通过改变季戊四醇上的取代基,得到了一系列零维到三维的镧系配位配合物。我们的结果表明,L(I)配体的配合物{Ln(4)L(I)(3)(NO(3))(12).nC(4)H(10)O}(infinity)(Ln = Nd、Eu、Tb、Er,n = 3或6)呈现出具有(8(3))(4)(8(6))(3)拓扑符号的双节点3,4-连接三维互穿配位聚合物。与L(I)相比,L(II)的配合物呈现出笼状同双核[Ln(2)L(II)(2)(NO(3))(6).2H(2)O].nH(2)O(Ln = Nd、Tb、Dy,n = 0或1)或螺旋一维配位{[ErL(II)(NO(3))(3).H(2)O].H(2)O}(infinity)聚合物。还详细研究了由用于荧光免疫分析的离子(Ln = Eu、Tb)形成的所得配合物的发光性质。值得注意的是,末端基团从苯到吡啶的细微变化不仅显著影响整体分子结构,还影响发光性质。