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A new family of platinum(II) complexes of the form PtLⁿSR have been prepared, where Lⁿ represents a cyclometalating, N^∧C^∧N-bound tridentate ligand and SR is a monodentate thiolate ligand. The complexes fall into two groups, those of PtL¹SR where HL¹ = 1,3-bis(2-pyridyl)benzene, and those of PtL²SR, where HL² = methyl 3,5-bis(2-pyridyl)benzoate. Each group consists of five complexes, where R = CH₃, C₆H₅, p-C₆H₄-CH₃, p-C₆H₄-OMe, p-C₆H₄-NO₂. These compounds, which are bright red, orange, or yellow solids, are formed readily upon treatment of PtLⁿCl with the corresponding potassium thiolate KSR in solution at room temperature. The replacement of the chloride by the thiolate ligand is accompanied by profound changes in the photophysical properties. A broad, structureless, low-energy band appears in the absorption spectra, not present in the spectra of PtLⁿCl. In the photoluminescence …