Origin of the Aggregation‐Induced Phosphorescence of Platinum(II) Complexes: The Role of Metal–Metal Interactions on Emission Decay in the Crystalline State

Discerning the origins of the phosphorescent aggregation-induced emission (AIE) from Pt(II) complexes is crucial for developing the broader range of photo-functional materials. Over the past few decades, several mechanisms of phosphorescent AIE have been proposed, however, not have been directly elucidated. Herein, we describe phosphorescence and deactivation processes of four class of AIE active Pt(II) complexes in the crystalline state based on experimental and theoretical investigation. These complexes show metal-to-ligand and/or metal-metal-to-ligand charge transfer emission in crystalline state with different heat resistance against thermal emission quenching. The calculated energy profiles including the minimum energy crossing point between S0 and T1 states were consistent with the heat resistant properties, which provided the mechanism for AIE expression. Furthermore, we have clarified the role of metal-metal interaction in AIE by comparing two computational models.