Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211 Geneva 4, Switzerland.
Inorg Chem. 2011 Sep 5;50(17):8588-97. doi: 10.1021/ic201156q. Epub 2011 Jul 28.
The structure and thermodynamic properties of lanthanide complexes with a new tripodal ligand L2 have been elucidated using different physicochemical methods. At stoichiometric ratios, the tetrahedral three-dimensional complexes with lanthanide cations are formed in acetonitrile with good stabilities. Despite minor structural changes comparing to previously investigated tripodal ligands, the resulting assembly exhibits different features revealed with the crystal structure of Eu(4)L2(4)(ClO(4))(11) (orthorhombic, Pbcn). Interestingly, the highly charged edifice contains an inner cage encapsulating a perchlorate anion. Such lanthanide mediated cage-like assemblies are rare, and may be of interest for different sensing applications. Indeed, the anionic guest can be exchanged with different anions. The related host-guest equilibria were investigated with NMR techniques. Various aspects of these reactions are qualitatively discussed.
采用不同的物理化学方法阐明了具有新型三脚架配体 L2 的镧系元素配合物的结构和热力学性质。在化学计量比下，在乙腈中形成具有镧系阳离子的四面体三维配合物，具有良好的稳定性。尽管与之前研究的三脚架配体相比结构略有变化，但所得组装体表现出不同的特征，这在 Eu(4)L2(4)(ClO(4))(11)（正交晶系，Pbcn）的晶体结构中得到揭示。有趣的是，高电荷的建筑包含一个内部笼，其中封装了一个高氯酸盐阴离子。这种镧系元素介导的笼状组装体很少见，可能对不同的传感应用感兴趣。实际上，可以用不同的阴离子交换阴离子客体。通过 NMR 技术研究了相关的主客体平衡。定性讨论了这些反应的各个方面。
