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Inorganics 2015, 3(4), 554-572; doi:10.3390/inorganics3040554

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
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)
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Abstract

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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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

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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