Electroluminescence of Tetradentate Pt(II) Complexes: O^N^N^O versus C^N^N^O Coordination

[Image: see text] Alkylation of one of the phenolic hydroxyl groups in a salen-type tetradentate ligand changes the coordination mode from O^N^N^O to the cyclometallating C^N^N^O type. The ligand was used to synthesize a new cyclometalated luminescent Pt(II) complex 2. While in solution the complex is poorly luminescent, in the solid state the emission is reinstated, which allowed one to evaluate complex 2 as a phosphorescent emitter in organic light-emitting diodes. 2 displays external quantum efficiency (EQE) = 9.1% and a maximum luminance of 9000 cd m(–2) in a vacuum-deposited device. We carried out comparative analysis of photo- and electroluminescence of complex 2 with O^N^N^O complex 1 and demonstrated that the similar luminescent properties of the O^N^N^O and C^N^N^O complexes are rather coincidental because they display different excited-state landscapes. Surprisingly, the two complexes display a dramatically different electrochemical behavior, with O^N^N^O coordination leading to the formation of a stable electropolymer but C^N^N^O coordination fully preventing electropolymerization.