Synthesis and Luminescence Properties of [Pt{4-(o-MeC6H4)- pzbipy}Cl]SbF6 [pzbipy = 6-2'-pyrazinyl)-2,22'-bipyridine]

The synthesis and characterisation of the 4-(o-R-C6H4)pzbipy [R = H, CH3 or CF3; pzbipy = 6-(2″- pyrazinyl)-2,2′-bipyridyl] ligands are described. Reaction of the 4-(o-MeC6H4)pzbipy ligand with [Pt(PhCN)2Cl2] in the presence of AgSbF6 affords [Pt{4-(o-MeC6H4)pzbipy}Cl]SbF6 as a marooncoloured microcrystalline solid. The [Pt{4-(o-MeC6H4)pzbipy}Cl]+ cation exhibits low intensity photoluminescence in dichloromethane that maximises at 543 nm and which is assigned to a 3MLCT excited state (τ = 20 ns). The emission spectrum of the cation was also recorded in a frozen DME {1 : 5:5 (v/v) DMF / MeOH / EtOH} glass; a highly structured band is observed with vibrational spacings of ca. 1400 cm−1, indicating emission from an intraligand 3π-π∗ state (τ = 11 μs). Variable temperature solid emission spectra show maxima that occur at significantly lower energies than is observed in fluid solution and that shift to the red when the temperature is lowered; specifically, λ (em)max is 674 nm at 280 K (τ = 80 ns) and 723 nm at 80 K (τ = 1.3 μs). Emission behaviour of this type is typical of emission from a metal-metal-ligand charge transfer (MMLCT) excited state that has its origins in dz² (Pt)-dz² (Pt) orbital interactions in the crystal.