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

Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry
Salauat R KiraevK Eszter Borbas

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. T...Continue Reading

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Citations

Mar 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Sebastiano Di PietroGiovanni Signore
Mar 11, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Daniel KovacsK Eszter Borbas
Nov 11, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Daniel KocsiK Eszter Borbas

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Methods Mentioned

BETA
X-ray
column chromatography

Software Mentioned

OriginPro

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