Ancillary Ligand Steric Effects and Cyclometalating Ligand Substituents Control Excited-State Decay Kinetics in Red-Phosphorescent Platinum Complexes

Achieving high-efficiency red phosphorescence remains a significant challenge, especially in cyclometalated platinum complexes where radiative rates are inherently slower than their iridium counterparts. In this work, six red-emitting cyclometalated platinum complexes of the formula Pt(C^∧N)[(Ar)acNac] (C^∧N is the cyclometalating ligand, and (Ar)acNac is an aryl-substituted β-ketoiminate ancillary ligand) were synthesized and characterized. Two C^∧N ligands were employed, 1-phenylisoquinoline (piq) and its cyano-substituted analogue 1-phenylisoquinoline-4-carbonitrile (piqCN), which both result in red phosphorescence in cyclometalated platinum complexes. These were paired with three (Ar)acNac ligands that are sterically differentiated via the <i>N</i>-aryl group, which is phenyl in the unsubstituted analogue (Ph)acNac and 2,6-dimethylphenyl or 2,6-diisopropylphenyl in the sterically encumbered analogues. An in-depth photophysical analysis of all compounds was performed and compared to the related compounds with the acetylacetonate (acac) ancillary ligand. While quantum yields are modest in the unsubstituted (Ph)acNac complexes, steric bulk on the β-ketoiminate has a pronounced effect on the excited-state dynamics and can lead to photoluminescence quantum yields of more than 0.50 in both solution and transparent polymer films, with the photoluminescence λ_max ∼ 630 nm. We show that both steric effects on the electron-rich β-ketoiminate ancillary ligands and the cyano substituent on the cyclometalating ligand play a role in achieving high-efficiency phosphorescence in the red region.