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­­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.

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


Authors

Alice C. Harnden



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

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Copyright Statement
This is the accepted version of the following article: Parker, David, Harnden, Alice C. & Batsanov, Andrei 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 which has been published in final form at https://doi.org/10.1002/chem.201900609. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.







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