Lanthanide Identity Governs Guest‐Induced Dimerization in Ln III [15‐MC N(L‐pheHA) ‐5]) 3+ Metallacrowns
Lanthanide Identity Governs Guest‐Induced Dimerization in Ln III [15‐MC N(L‐pheHA) ‐5]) 3+ Metallacrowns
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镧系元素控制客体 - Ln III 中诱导的二聚化 [15 - MC N(L - pheHA) - 5]) 3 金属冠
DOI：
10.1002/chem.202103263
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Arena, Giuseppe
中科院分区：
文献类型：
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作者：
Sgarlata, Carmelo;Schneider, Bernadette L.;Zito, Valeria;Migliore, Rossella;Tegoni, Matteo;Pecoraro, Vincent L.;Arena, Giuseppe
由于稀土元素具有相似的化学性质和配位性质，一系列含镧金属配位化合物经常被认为是结构相似的。在手性(LnIII[15-MCN(L-pheHA)-5])3+金属杂多酸(MC)的情况下，在中性pH溶液中，以二羧酸盐客体(Muconate)为模板的二聚体的形成与MC的中心稀土元素的同一性有关。量热数据和核磁共振扩散研究表明，以较大或较小的稀土元素为中心金属的MC只形成单体主客体络合物，而具有中间稀土元素的类似物(如Eu，Gd，Dy)参与形成二聚体主客体空间。整个系列中二聚事件的驱动力被认为是形成高度稳定的MC(较大的稀土元素)和最佳连接的桥联客体(较小的稀土元素)之间的竞争。
Series of lanthanide‐containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (LnIII[15‐MCN(L‐pheHA)‐5])3+metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host‐guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host‐guest‐host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides).