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
| Autor: | Fabrice Pointillart, Saskia Speed, Bertrand Lefeuvre, François Riobé, Stéphane Golhen, Boris Le Guennic, Olivier Cador, Olivier Maury, Lahcène Ouahab |
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| Jazyk: | angličtina |
| Rok vydání: | 2015 |
| Předmět: | |
| Zdroj: | Inorganics, Vol 3, Iss 4, Pp 554-572 (2015) |
| Druh dokumentu: | article |
| ISSN: | 2304-6740 84542446 |
| DOI: | 10.3390/inorganics3040554 |
| Popis: | 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. |
| Databáze: | Directory of Open Access Journals |
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