Luminescent 2-phenylbenzothiazole cyclometalated PtII and IrIII complexes with chelating P^O ligands

Two series of cyclometalated PtII and IrIII complexes with general formulas [Pt(pbt){PPh2(R)-κP,O}] (2a–2c) and [Ir(pbt)2{PPh2(R)-κP,O}] (3a–3c), where Hpbt is 2-phenylbenzothiazol and PPh2(R) is a diphenylphosphino donor functionalized deprotonated acid (R = o-C6H4CO2a, o-C6H4SO3b, CH2CH2CO2c) are presented. The structures of 1, 2a–2c, 3a and 3b were confirmed by single X-ray diffraction analyses, and the intermolecular interactions in 2a were studied using Hirshfeld surface analysis and non-covalent interaction (NCI) methods on its X-ray structure. Their photophysical properties were investigated by absorption and emission analyses [CH2Cl2, solid (298, 77 K) and doped polystyrene (PS) films], supported by TD-DFT calculations on 1, 2a–2c and 3a. The PtII complexes exhibit bright phosphorescence in the region 525–542 nm, ascribed to a mixed 3IL/3MLCT excited state with a predominant 3IL contribution. The IrIII derivatives (3a–3c) show orange photoluminescence (535–584 nm, 298 K), blue shifted at 77 K (527–560 nm), originated from the admixture of 3IL/3MLCT/3LLCT excited states. Interestingly, the photoluminescence quantum yields of the Pt complexes 2a–2c (φ = 46.5–66.5%) in PS films are remarkably higher than those of the corresponding iridium complexes (φ = 17.3–32%) and the precursor 1 (φ = 17%). The calculated 3MC-3IL/3MLCT energy gap for 2a and 3a accounts for the higher quantum yield of the Pt in relation to the Ir complex.