Calix[4]azacrowns as novel molecular scaffolds for the generation of visible and near-infrared lanthanide luminescence

Inorganic Chemistry
Issam OueslatiUwe Pischel

Abstract

Two calix[4]azacrowns, capped with two aminopolyamide bridges, were used as ligands for the complexation of lanthanide ions [Eu(III), Tb(III), Nd(III), Er(III), La(III)]. The formation of 1:2 and 1:1 complexes was observed, and stability constants, determined by UV absorption and fluorescence spectroscopy, were found to be generally on the order of log beta(11) approximately 5-6 and log beta(12) approximately 10. The structural changes of the ligands upon La(III) complexation were probed by 1H NMR spectroscopy. The two ligands were observed to have opposite fluorescence behaviors, namely, fluorescence enhancement (via blocking of photoinduced electron transfer from amine groups) or quenching (via lanthanide-chromophore interactions) upon metal ion complexation. Long-lived lanthanide luminescence was sensitized by excitation in the pi,pi band of the aromatic moieties of the ligands. The direct involvement of the antenna triplet state was demonstrated via quenching of the ligand phosphorescence by Tb(III). Generally, Eu(III) luminescence was weak (Phi(lum) </= 0.01%) and much shorter lived (tau(lum) = 0.36 ms) than the Tb(III) emission. The latter, on the other hand, reached lifetimes of up to 2.60 ms and quantum yields as high a...Continue Reading

References

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Citations

Apr 26, 2008·Journal of Fluorescence·Issam OueslatiMário N Berberan-Santos
Jun 28, 2017·Luminescence : the Journal of Biological and Chemical Luminescence·Lina Zhao
Feb 11, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Chang FengGuang-Ming Li
Sep 28, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Moheddine WehbieStéphane Pellet-Rostaing
Aug 11, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiao-Fei QiaoBing Yan
Jul 10, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Fengming ZhangGuangming Li
Mar 19, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Brendan W EnnisMassimiliano Massi
Apr 17, 2012·Journal of the American Chemical Society·Ana de Bettencourt-DiasSebastian Bauer

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