Controlled formation of desired lanthanide supramolecular complexes is challenging because of the difficulties in predicting coordination geometry, as well as a labile coordination number. Herein, we explore the effect of ionic radii and linker length on supramolecular species formation. A helicate-to-tetrahedron transformation occurred between [Ln₂L1₃] and [Ln₄L1₆] (Ln = La, Sm, Eu, Gd, Tb and Lu). For six lanthanide ions, the unfavored tetrahedron [La₄L1₆] can only be observed in a concentrated mixture with the helicate [La₂L1₃] where no pure [La₄L1₆] species was isolated via crystallization. For Sm, Eu, Gd, Tb, the [Ln₄L1₆] supramolecular tetrahedron can be isolated via crystallization from diisopropyl ether. A similar result was also observed for Lu, but the tetrahedral structure was found to be relatively stable and transformed back to [Lu₂L1₃] much slower upon dissolution. No tetrahedron formation was observed with L3 giving rise to only [Ln₂L3₃] species, in which L3 contains a longer and more flexible linker compared with that of L1. Results show that the supramolecular transformation in these systems is governed by both the ionic radii as well as the ligand design. Special focus is on both [Eu₂L1₃] and [Eu₄L1₆] which form chiral entities and exhibit interesting circular polarized luminescence.

由于难以预测配位几何以及不稳定的配位数，因此所需镧系元素超分子配合物的受控形成具有挑战性。在此，我们探讨了离子半径和接头长度对超分子物种形成的影响。在[Ln ₂ L1 ₃ ]和[Ln ₄ L1 ₆ ]之间发生螺旋到四面体的转变（Ln = La、Sm、Eu、Gd、Tb和Lu）。对于六个镧系元素离子，不利的四面体 [La ₄ L1 ₆ ] 只能在与螺旋线 [La ₂ L1 ₃ ] 的浓缩混合物中观察到，其中没有纯 [La ₄ L1 ₆] 物种通过结晶分离。对于Sm、Eu、Gd、Tb，[Ln ₄ L1 ₆ ]超分子四面体可以通过从二异丙醚中结晶分离。对于 Lu 也观察到类似的结果，但发现四面体结构相对稳定并且在溶解时转变回 [Lu ₂ L1 _{3 ] 的速度要慢得多。}没有观察到L3形成四面体，仅产生 [Ln ₂ L3 ₃ ] 物种，其中L3包含比L1更长且更灵活的接头. 结果表明，这些系统中的超分子转化受离子半径和配体设计的影响。特别关注 [Eu ₂ L1 ₃ ] 和 [Eu ₄ L1 ₆ ]，它们形成手性实体并表现出有趣的圆偏振发光。