Synthesis, photophysical and electrophosphorescent properties of fluorene-based platinum(II) complexes.

A series of platinum(II) complexes bearing tridentate cyclometalated C^N^N (C^N^N=6-phenyl-2,2'-bipyridine and π-extended R-C^N^N=3-[6'-(naphthalen-2''-yl)pyridin-2'-yl]isoquinoline) ligands with fluorene units have been synthesised and their photophysical properties have been studied. The fluorene units are incorporated into the cyclometalated ligands by a Suzuki coupling reaction. An increase in the π-conjugation of the cyclometalated ligands confers favourable photophysical properties compared to the 6-phenyl-2,2'-bipyridine analogues. The fluorene-based platinum(II) complexes display vibronic-structured emission bands with λ(max)=558-601 nm, and high emission quantum yields up to 0.76 in degassed dichloromethane. Their emissions are tentatively assigned to excited states with mixed (3)IL/(3)MLCT parentage (IL=intraligand, MLCT=metal-to-ligand charge transfer). The crystal structures of these platinum(II) complexes reveal extensive Pt(II)···π and/or π-π interactions. The fluorene-based platinum(II) complexes are soluble in organic solvents, have high thermal stability with decomposition temperature >350 °C, and can be thermally vacuum-sublimed or solution-processed as phosphorescent dopants for the fabrication of organic light-emitting diodes (OLEDs). A monochromic OLED with 3d as dopant (2 wt%) fabricated by vacuum deposition gave a current efficiency of 14.7 cd A(-1) and maximum brightness of 27000 cd m(-2). A high current efficiency (9.2 cd A(-1)) has been achieved in a solution-processed OLED using complex 3f (5 wt%) doped in a PVK (poly(9-vinylcarbazole)) host.