Lanthanide(III) Complexes of Cyclen Triacetates and Triamides Bearing Tertiary Amide-Linked Antennae

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ID: 267349
2020
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Abstract
The coordination compounds of the trivalent lanthanide ions (Ln(III)) have unique photophysical properties. Ln(III) excitation is usually performed through a light-harvesting antenna. To enable Ln(III)-based emitters to reach their full potential, an understanding of how complex structure affects sensitization and quenching processes is necessary. Here, the role of the linker between the antenna and the metal binding fragment was studied. Four macrocyclic ligands carrying coumarin 2 or 4-methoxymethylcarbostyril sensitizing antennae linked to an octadentate macrocyclic ligand binding site were synthesized. Complexation with Ln(III) (Ln = La, Sm, Eu, Gd, Tb, Yb and Lu) yielded species with overall −1, 0, or +2 and +3-charge. Paramagnetic 1H NMR spectroscopy indicated subtle differences between the coumarin- and carbostyril-carrying Eu(III) and Yb(III) complexes. Cyclic voltammetry showed that the effect of the linker on the Eu(III)/Eu(II) apparent reduction potential was dependent on the electronic properties of the N-substituent. The Eu(III), Tb(III) and Sm(III) complexes were all luminescent. Coumarin-sensitized complexes were poorly emissive; photoinduced electron transfer was not a major quenching pathway in these species. These results show that seemingly similar emitters can undergo very different photophysical processes, and highlight the crucial role the linker can play.
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kiraev2020moleculeslanthanide(iii) Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Salauat R. Kiraev;Emilie Mathieu;Fiona Siemens;Daniel Kovacs;Ellen Demeyere;K. Eszter Borbas;Kiraev, Salauat R.;Mathieu, Emilie;Siemens, Fiona;Kovacs, Daniel;Demeyere, Ellen;Borbas, K. Eszter;
Journal molecules
Year 2020
DOI
10.3390/molecules25225282
URL
https://doi.org/10.3390/molecules25225282
Keywords
luminescence electrochemistry coumarin lanthanide do3a carbostyril

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