A series of heteroleptic binuclear Pd(ii) and Pt(ii) complexes, [M(bdts)]2(μ-dppa)2(M = Pd (3) and Pt (4); dppa = 1,2-bis(diphenylphosphino)acetylene = Ph2PCCPPh2; bdts = 1,2-benzenedithiolate (bdt: a), 3,4-toluenedithiolate (tdt: b) and 1,4-dichloro-2,3-benzenedithiolate (Cl2bdt: c), containing two square-planar MP2S2cores were prepared using (MCl2)2(μ-dppa)2(M = Pd (1) and Pt (2)) and the corresponding 1,2-benzenedithiols, and characterized by spectroscopic methods including FT-IR, Raman, UV-vis, MALDI-TOF-MS, 31P{1H} and/or 195Pt{1H} NMR spectroscopy. X-Ray crystal structure analyses for complexes 3and 4revealed that C1C2C4C3 is twisted in two ways with a torsion angle of 21.6–30.7° for 3a, 3b, 4aand 4band about 42° for 3cand 4c, and that their crystals are racemic mixtures. Due to the more electronegative chloride atoms in the ligand, complexes 3cand 4cshow higher ν(M–S) vibrational frequencies in their Raman spectra, smaller spin–spin coupling constants (JPt–P) in their 195Pt{31P} NMR spectra and higher anodic potentials (Epa) in their cyclic voltammograms than complexes 3a, 3b, 4aand 4b. Moreover, only complex 4ccontaining the chlorinated ligand and Pt(ii) ion exhibits luminescence (λob= 610 nm and λex= 440 nm) in the solid state at 298 K. This emissive transition can be assigned as the d–π*dithiolatemetal-to-ligand charge transfer (MLCT) and the feasibility of this spin-forbidden transition is ascribed to the effective spin–orbit coupling of ligand ccontaining heavy chloride atoms and the large spin–orbit coupling in Pt(ii). [ABSTRACT FROM AUTHOR]