New N,N’-bis(4-((4-alkoxybenzoyl)oxy)phenyl)-1,4-diaza-1,3-butadiene (L) ligands, obtained by condensation of 4-((alkoxybenzoyl)oxy)anilines and glyoxal, were complexed to different [ReX(CO)(3)] fragments to give the complexes [ReX(L)(CO)(3)] (X = Cl, Br, I) and [Re(CF3SO3)(L)(CO)(3)]. THF. The chloro and bromo complexes were obtained by direct reaction of the ligands with [ReX(CO)(5)] (X = Cl, Br), while the iodo and triflato derivatives were obtained via metathesis of the chloro or bromo precursors with potassium iodide or silver triflate respectively. The liquid-crystalline behavior of the ligands and the related rhenium complexes has been studied by means of optical microscopy, differential scanning calorimetry, and small angle X-ray diffraction. Nematic and smectic C phases were observed when the coordinated counteranions were Cl, Br, and I, respectively; the triflato derivatives were not mesomorphic.