Luminescent halido(aryl) Pt(IV) complexes obtained via oxidative addition of iodobenzene or diaryliodonium salts to bis-cyclometalated Pt(II) precursors.

The synthesis of bis-cyclometalated halido(aryl) Pt(IV) complexes [PtX(Ar)(C^N)2], with C^N = cyclometalated 4-(tert-butyl)-2-phenylpyridine (bppy), 2-(p-tolyl)pyridine (tpy), 2-(2-thienyl)pyridine (thpy), or 1-phenylisoquinoline (piq), X = I, Cl, or F, and Ar = Ph (for all C^N ligands) or t-BuPh (for C^N = tpy), and the photophysical properties of the chlorido and fluorido series is reported. The oxidative addition of iodobenzene to cis-[Pt(C^N)2] precursors is demonstrated to occur in MeCN under irradiation with visible light to give complexes [PtI(Ph)(C^N)2], presumably involving radical species that also produce the activation of the solvent to give cyanomethyl complexes [PtI(CH2CN)(C^N)2]. The introduction of an aryl ligand can also be achieved by reacting cis-[Pt(C^N)2] with (Ar2I)PF6 (Ar = Ph, t-BuPh), which affords cationic intermediates of the type [Pt(Ar)(C^N)2(NCMe)]+. The subsequent addition of an iodide or chloride salt gives the corresponding iodido- or chlorido(aryl) complexes. The fluorido(aryl) derivatives can be obtained from the iodido complexes by halide exchange using AgF. The chlorido- and fluorido(aryl) complexes display intense phosphorescence in deaerated CH2Cl2 solution and poly(methyl methacrylate) (PMMA) films at 298 K from triplet excited states primarily localized on the cyclometalated ligands (3LC) with a small MLCT admixture. Compared with the chlorido complexes, the fluorido derivatives consistently present significantly shorter emission lifetimes and higher radiative and nonradiative rate constants due to a greater MLCT contribution to the emissive state. In contrast, the introduction of the t-BuPh group did not induce significant changes in radiative rates with respect to the phenyl complexes.