Paramagnetic Lanthanide NMR Probes Signalling Changes in Zinc Concentration by Emission and Chemical Shift: A Proof of Concept Study,Chemistry - A European Journal

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Paramagnetic Lanthanide NMR Probes Signalling Changes in Zinc Concentration by Emission and Chemical Shift: A Proof of Concept Study
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-04-04 , DOI: 10.1002/chem.201900609
Alice C. Harnden ₁ , Andrei S. Batsanov ₁ , David Parker ₁

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A zinc‐selective probe based on a set of rare earth complexes of a modified DO3A macrocyclic ligand incorporating a tris‐pyridylamine (TPA) moiety has been structurally characterised in solution and in the solid‐state. One pyridine group possesses a tert‐butyl substituent to serve as an NMR reporter group. The mono‐capped square‐antiprismatic Dy complex has a long bond (2.83 Å) to an apical N atom (pK_a 5.70 Eu) and binds to one water molecule on zinc binding. Zinc binding is reversible and involves all of the exocyclic ligand N donors; it is signalled by large (ratiometric) changes in Eu emission intensity, and by dramatic changes in the size (>50 ppm) and sign of the chemical shift of the paramagnetically shifted tBu resonances in Tb, Dy and Tm complexes. Slow trans‐metallation was observed, leading to formation of an unusual di‐zinc species in which one zinc ion is seven‐coordinate and the other is six‐coordinate.

中文翻译：

顺磁性镧系元素NMR探针通过发射和化学位移指示锌浓度的变化：概念研究的证明

锌选择性探针基于在溶液中和在固态中的结构特征，该探针基于结合了三吡啶胺（TPA）部分的修饰的DO3A大环配体的稀土配合物。一个吡啶基具有一个叔丁基取代基，可作为NMR报告基团。单峰方形反棱Dy络合物与顶部的N原子（p K_为5.70 Eu）具有长键（2.83Å），并与一个水分子结合锌键。锌结合是可逆的，并且涉及所有的环外配体N供体。Eu发射强度的较大变化（比率），尺寸（> 50 ppm）的显着变化以及顺磁性移动的t的化学位移的信号表明了这一点。Tb，Dy和Tm络合物中的Bu共振。观察到缓慢的反金属化作用，导致形成不寻常的二锌物种，其中一个锌离子为七坐标，另一个锌离子为六坐标。

更新日期：2019-04-04

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