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Structural and Physical Investigations of Coordination Complexes Involving Pyridylethylenedithio–Tetrathiafulvalene Ligands Decorated with Cyanoethylsulfanyl and Cyanoethylselanyl Moieties
Author(s) -
Douib Haiet,
Pointillart Fabrice,
Lefeuvre Bertrand,
Golhen Stéphane,
Cador Olivier,
Le Guennic Boris,
Gouasmia Abdelkrim,
Ouahab Lahcène
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601241
Subject(s) - tetrathiafulvalene , chemistry , crystallography , nitrile , metal , stereochemistry , ion , crystal structure , metal ions in aqueous solution , single crystal , crystal (programming language) , coordination complex , density functional theory , molecule , computational chemistry , organic chemistry , programming language , computer science
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.