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High-spin iron(II) as a semitransparent partner for tuning europium(III) luminescence in heterodimetallic d-f complexes

Edder, Carine
Bünzli, Jean-Claude
Published in Chemistry - A European Journal. 2001, vol. 7, no. 14, p. 3014-3024
Abstract The segmental ligand 2-[6-(N,N-diethylcarbamoyl)pyridin-2-yl]-1,1'-dimethyl-5,5'-methylene-2'-(6-methylpyridine-2-yl)bis[1H-benzimidazole] (L3) reacts with a stoichiometric mixture of LnIII (Ln = La, Eu, Gd) and M(II) (M = Zn, Fe) in acetonitrile to produce selectively the heterodimetallic triple-stranded helicates (HHH)-[LnM(L3)3]5+. In these complexes, M(II) is pseudooctahedrally coordinated by the three wrapped bidentate binding units, thus forming a noncovalent tripod which organizes the three unsymmetrical tridentate segments to give ninefold coordination to LnIII. The introduction of a methyl group at the 6 position of the terminal pyridine in L3 sterically reduces the complexing ability of the bidentate segment for M(II). Spectroscopic (ESI-MS, UV/Vis/NIR, NMR), magnetic and electrochemical measurements show that 1) the head-to-head-to-head triple helical complexes (HHH)-[LnM(L3)3]5+ are quantitatively formed in solution only for ligand concentrations larger than 0.01 M, 2) FeII adopts a pure high-spin electronic configuration in (HHH)-[LnFe(L3)3]5+ and 3) the FeII/FeIII oxidation process is prevented by steric constraints. Detailed photophysical studies of (HHH)-[Eu-Zn(L3)3]5+ confirm that the pseudotricapped trigonal-prismatic lanthanide coordination site is not affected by the methyl groups bound to the terminal pyridine, thus leading to significant Eu-centered emission upon UV irradiation. In (HHH)-[EuFe(L3)3]5+, a resonant intramolecular Eu-->Fe(II)hs energy transfer partially quenches the Eu-centered luminescence; however, the residual red emission demonstrates that high-spin iron(II) is compatible with the sensitization of Eu(III) in heterodimetallic d-f complexes. The influence of the electronic configuration of Fe(II) on the efficiency of Eu(III)-->Fe(II) energy-transfer processes is discussed together with its consequence for the design of optically active spin-crossover supramolecular devices.
Keywords Energy transferIronHelical structuresHeterodimetallic complexesLanthanidesLuminescence
PMID: 11495428
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EDDER, Carine et al. High-spin iron(II) as a semitransparent partner for tuning europium(III) luminescence in heterodimetallic d-f complexes. In: Chemistry - A European Journal, 2001, vol. 7, n° 14, p. 3014-3024. https://archive-ouverte.unige.ch/unige:2348

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Deposited on : 2009-08-06

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