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In this study, a couple of tetradentate Pt(II) enantiomers ((−)-1 and (+)-1) and a couple of tetradentate Pt(IV) enantiomers ((−)-2 and (+)-2) containing fused 5/6/6 metallocycles have been synthesized by controlling reaction conditions. Two valence forms could transform into each other through mild chemical oxidants and reductants. Single-crystal X-ray diffraction confirms the structures of (−)-1 and (−)-2. The coordination sphere of the Pt(II) cation in (−)-1 displays a distorted square-planar geometry and a platinum centroid helix chirality. In contrast, the structure of (−)-2 reveals a distorted octahedral geometry. The solution and the solid of (−)-1 are highly luminescent. Complex (−)-1 shows a prominent aggregation-induced emission enhancement (AIEE) behavior in DMSO/water solution with emission quantum yield (Φem) up to 73.2%. Furthermore, highly phosphorescent Pt(II) enantiomers exhibit significant circularly polarized luminescence (CPL) with a dissymmetry factor (glum) of order 10−3 in CH2Cl2 solutions at room temperature. Symmetrically appreciable CPL signals are observed for the enantiomers (−)-1 and (+)-1.

Two new tfmpiq-based bis-cyclometalated iridium(III) complexes, [(tfmpiq)2Ir(imdzppo)] (2a) and [(tfmpiq)2Ir(idzpo)] (2b) (where tfmpiq = 1-(4-(trifluoromethyl)phenyl)isoquinoline, imdzppo = 2-(imidazo[1,2-a]pyridin-2-yl)phenol, idzpo = 2-(2H-indazol-2-yl)phenol), have been synthesized and fully characterized. The single crystal structure of 2b has been determined. The relationship between the structures and photophysical properties of both complexes are considered, and the DFT calculations have been used to further support the deduction. These Ir(III) complexes emit red light with quantum yields of 39.9–51.9% in degassed CH2Cl2 solution at room temperature. Also, their emission originates from a hybrid 3MLCT/3LLCT/3LC excited state. All these results show that iridium(III) complexes 2a-2b are suitable for red-phosphorescent materials in OLEDs.