The remarkable luminescence properties of the platinum(II) complex of 1, 3-di (2-pyridyl) benzene, acting as a terdentate NCN-coordinating ligand cyclometalated at C2 of the benzene ring ([PtL1-Cl]), have been investigated, together with those of two new 5-substituted analogues [(PtLCl)-Cl-2] and [(PtLCl)-Cl-3] {HL2 = methyl-3,5-di(2-pyridyl)benzoate; HL3 = 3,5-di(2-pyridyl)toluenel. All three complexes are intense emitters in degassed solution at 298 K (lambdamax 480-580 nm; phi(lum), = 0.60, 0.58, and 0.68 in CH2Cl2), displaying highly structured emission spectra in dilute solution, with lifetimes in the microsecond range (7.2, 8.0, and 7.8,us). On the basis of the very small Stokes shift, the highly structured profiles, and the relatively long lifetimes, the emission is attributed to an excited state of primarly 3pi-pi* character. At concentrations >1 X 10(-5) M, structureless excimer emission centered at ca. 700 nm is observed. The X-ray crystal structure of [PtL Cl-2] is also reported.