Abstract

The photophysical properties of square planar Pt(II) complexes are often strongly dependent on their self‐assembly modes and intermolecular Pt⋯Pt interactions. Controlling these interactions is important to achieve valuable properties for various applications, such as light‐emitting diodes and environmental sensing devices. Herein, a series of highly luminescent ionic Pt(II) complexes with tunable emission colors are reported, by controlling the molecular structures and interactions in solid state. Four ionic Pt(II) complexes, with a general formula [Pt(C^N)(N^N)]+X− (C^N = 2‐phenylpyridine or 2‐(2,4‐difluorophenyl)pyridine; N^N = 2,2′‐bipyridine; X−= chloride (Cl−) or tetraphenylborate (BPh4−), are designed, synthesized, and characterized. Due to the presence of intermolecular Pt⋯Pt interactions, strong metal–metal‐to‐ligand charge transfer (MMLCT) emissions are recorded in all four complexes with color changing from green to deep red in solid state. A high photoluminescence quantum efficiency (PLQE) of 81% is achieved for one of the complexes containing large BPh4− anions, due to the site isolation effects. Detailed structural and photophysical characterizations reveal a clear correlation between the stacking of these Pt(II) complexes and their photophysical properties, which can be well regulated by the molecular structures and counter‐anions.

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