Structural and Physical Investigations of Coordination Complexes Involving Pyridylethylenedithio–Tetrathiafulvalene Ligands Decorated with Cyanoethylsulfanyl and Cyanoethylselanyl Moieties

The two new ligands 4,5‐bis(2‐cyanoethylthio)‐4′,5′‐(4‐pyridylethylene‐1,2‐dithio)tetrathiafulvalene (L1) and 4,5‐bis(2‐cyanoethylseleno)‐4′,5′‐(4‐pyridylethylene‐1,2‐dithio)tetrathiafulvalene (L2) have been elaborated and used to synthesize five new coordination complexes of transition‐metal ions, namely, [Mn2(hfac)4(L1)2]2 (1; hfac– = 1,1,1,5,5,5‐hexafluoroacetylacetonate), [Cd(hfac)2(L1)2]·2CHCl3 (2), [Cu(hfac)2(L1)2] (3), [Co(hfac)2(L1)2]·2C6H14 (4) and [Mn(hfac)2(L2)2]·2C6H14 (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 L1 is coordinated to the MnII ions through two different pyridyl and nitrile functionalizations. The photophysical properties of the ligands L1 and L2 were studied in solution and rationalized with time‐dependent density functional theory calculations.