Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 36, Pages 5630-5639Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201601241
Keywords
Sulfur heterocycles; Transition metals; N ligands; Structure elucidation; Density functional calculations
Categories
Funding
- Agence Nationale de la Recherche [ANR-13-BS07-0022-01]
- Ministry of Higher education and Scientific Research: Directorate General for Scientific research and Technological Development
- French GENCI-CINES center [x2015080649]
- Centre National de la Recherche Scientifique (CNRS), Rennes Metropole, Universite de Rennes 1, Region Bretagne
- FEDER
- Agence Nationale de la Recherche (ANR) [ANR-13-BS07-0022] Funding Source: Agence Nationale de la Recherche (ANR)
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The two new ligands 4,5-bis(2-cyanoethylthio)-4',5'-(4-pyridylethylene-1,2-dithio)tetrathiafulvalene (L-1) and 4,5-bis(2-cyanoethylseleno)-4',5'-(4-pyridylethylene-1,2-dithio)tetrathiafulvalene (L-2) have been elaborated and used to synthesize five new coordination complexes of transition-metal ions, namely, [Mn-2(hfac)(4)(L-1)(2)](2) (1; hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate), [Cd(hfac)(2)(L-1)(2)].2CHCl(3) (2), [Cu(hfac)(2)(L-1)(2)] (3), [Co(hfac)(2)(L-1)(2)].2C(6)H(14) (4) and [Mn(hfac)(2)(L-2)(2)].2C(6)H(14) (5), which were characterized by single-crystal X-ray diffraction. Compounds 2-5 were identified as mononuclear complexes with different crystal packing depending on the nature of the metal centre. On the contrary, compound 1 was identified as a cyclic tetranuclear complex in which L-1 is coordinated to the Mn-II ions through two different pyridyl and nitrile functionalizations. The photophysical properties of the ligands L-1 and L-2 were studied in solution and rationalized with time-dependent density functional theory calculations.
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