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Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio)-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand

1
Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-UR1, Université de Rennes 1, 35042 Rennes Cedex, France
2
Laboratoire de Chimie de l’ENS-LYON-UMR 5182, 46 Allée d’Italie, 69364 Lyon Cedex 07, France
*
Author to whom correspondence should be addressed.
Academic Editors: Stephen Mansell and Steve Liddle
Inorganics 2015, 3(4), 554-572; https://doi.org/10.3390/inorganics3040554
Received: 15 October 2015 / Revised: 13 November 2015 / Accepted: 23 November 2015 / Published: 3 December 2015
(This article belongs to the Special Issue Rare Earth and Actinide Complexes)
The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L) and the metallo-precursors Ln(hfac)3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac)6(L)]·(CH2Cl2)·(C6H14)0.5 (LnIII = DyIII (1) and YbIII (2)). The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF) core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital)→LUMO (Lowest Unoccupied Molecular Orbital) Intra-Ligand Charge Transfer (ILCT) transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties. View Full-Text
Keywords: lanthanides; tetrathiafulvalene; magnetism; photo-physics; TD-DFT calculations lanthanides; tetrathiafulvalene; magnetism; photo-physics; TD-DFT calculations
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Pointillart, F.; Speed, S.; Lefeuvre, B.; Riobé, F.; Golhen, S.; Le Guennic, B.; Cador, O.; Maury, O.; Ouahab, L. Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio)-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand. Inorganics 2015, 3, 554-572.

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