a b s t r a c t This paper presents a combined experimental and computational study of Ru(II) carbonyl complexes con-taining thiosemicarbazone ligands. Five novel [Ru(H/Cl)(L)(PPh 3) 2 ] complexes have been obtained and characterized by IR, 1 H, 13 C, 31 P NMR, UV–Vis spectroscopy and X-ray crystallography. Their electronic structures have been determine d using the density functional theory (DFT) method and employed for a discussion of their properties. The donor–acceptor properties of the ligands were correlated with the substitu ent positions on the benzene ring. The luminescence properties of the complexes have also been examine d.