A new type of multidentate ligand with both acetylacetonate and bis(2-pyridyl) units on the 1,3-dithiole moiety, 3-[2-(dipyridin-2-yl-methylene)-5-methylsulfanyl-[1,3]dithiol-4-ylsulfanyl]-pentane-2, 4-dione (L), has been prepared. Through reactions of the ligand with Re(CO)(5)X (X = Cl, Br), new rhenium(I) tricarbonyl complexes ClRe(CO)(3)(L) (2) and BrRe(CO)(3)(L) (3), have been obtained. With the use of 2 or 3 as the precursors, the further reactions with (Tp(Ph2))Co(OAc)(Hpz(Ph2)) (Tp(Ph2) = hydrotris(3,5-diphenylpyrazol-1-yl)borate); Hpz(Ph2) = 3,5-diphenyl-pyrazole) or M(OAc)(2) (M = Mn, Zn), afford four new heteronuclear complexes: ClRe(CO)(3)(L)Co(Tp(Ph2)) (4), BrRe(CO)(3)(L)Co(Tp(Ph2)) (5), [ClRe(CO)(3)(L)](2)Mn(CH3OH)(2) (6) and [ClRe(CO)(3)(L)](2)Zn(CH3OH)(2) (7), respectively. Crystal structures of complexes 2 and 4-7 have been determined by X-ray diffraction. Their absorption spectra, photoluminescence and magnetic properties have been studied. (C) 2011 Elsevier B.V. All rights reserved.