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Title

Lanthanide triple helical complexes with a chiral ligand derived from 2,6-pyridinedicarboxylic acid

Authors
Muller, Gilles
Schmidt, Catherine
Jiricek, Jan
Riehl, James P.
Buenzli, Jean-Claude G.
Published in Journal of the Chemical Society. Dalton Transactions. 2001, no. 18, p. 2655-2662
Abstract The ligand 3-[2,6-bis(diethylcarbamoyl)pyridine-4-yl]-N-(tert-butoxycarbonyl)alanine methyl ester (L4) bearing a chiral group in the 4-position of the pyridine ring has been synthesised and its interaction with trivalent lanthanide ions studied. L4 yields stable [Ln(L4)3]3+ complexes in acetonitrile, with log3 in the range 19–20. The specific rotary dispersion of the complexes is about ten times as large as that of the ligand alone, consistent with triple helical structures in solution. NMR data show the presence of only one time-averaged species in acetonitrile solution with a trigonal symmetry, that is, the helical P M interconversion is fast on the NMR time scale. Circularly polarised luminescence on the Eu and Tb triple helical complexes displays weak effects, pointing to only a small diastereomeric excess in solution. High resolution luminescence spectra of the Eu complex in the solid state reveal a local symmetry derived from a trigonal arrangement around the metal ion and the long 5D0 lifetime (1.58 ms) is indicative of the absence of water molecules bound in the inner co-ordination sphere. Energy transfer processes in the luminescent Eu and Tb triple helical complexes are discussed.
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Other version: http://www.rsc.org/ej/DT/2001/b102728j.pdf
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MULLER, Gilles et al. Lanthanide triple helical complexes with a chiral ligand derived from 2,6-pyridinedicarboxylic acid. In: Journal of the Chemical Society. Dalton Transactions, 2001, n° 18, p. 2655-2662. https://archive-ouverte.unige.ch/unige:2351

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Deposited on : 2009-08-06

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