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

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.