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Versatile Para‐Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function

Starck, Matthieu and Fradgley, Jack D. and De Rosa, Davide F. and Batsanov, Andrei S. and Papa, Maria and Taylor, Michael J. and Lovett, Janet E. and Lutter, Jacob C. and Allen, Matthew J. and Parker, David (2021) 'Versatile Para‐Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function.', Chemistry – A European Journal, 27 (71). pp. 17921-17927.


A series of cationic and neutral p−Br and p−NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C−N and C−C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transition accompanied by a reduction in the Eu−Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p-substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions.

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Publisher statement:This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Date accepted:27 October 2021
Date deposited:27 January 2022
Date of first online publication:20 December 2021
Date first made open access:27 January 2022

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