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

Parker, David; Harnden, Alice C.; Batsanov, Andrei S.

Abstract

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 (2.83Å) to an apical N atom (pKa 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 7‐coordinate and the other is six‐coordinate.

Citation

Parker, D., Harnden, A. C., & Batsanov, A. S. (2019). ­­Paramagnetic Lanthanide NMR Probes Signalling Changes in Zinc Concentration by Emission and Chemical Shift: A Proof of Concept Study. Angewandte Chemie, 25(24), 6212-6225. https://doi.org/10.1002/chem.201900609

• Journal Article Type: Article
• Acceptance Date: Mar 11, 2019
• Online Publication Date: Apr 4, 2019
• Publication Date: Apr 24, 2019
• Deposit Date: Mar 27, 2019
• Publicly Available Date: Apr 4, 2020
• Journal: Angewandte Chemie
• Print ISSN: 0044-8249
• Electronic ISSN: 1521-3757
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 25
• Issue: 24
• Pages: 6212-6225
• DOI: https://doi.org/10.1002/chem.201900609
• Public URL: https://durham-repository.worktribe.com/output/1305139