Cyclometallated platinum(II) complexes of 1,3-di(2-pyridyl)benzenes: tuning excimer emission from red to near-infrared for NIR-OLEDs

The Pt(II) complex N boolean AND(CN)-N-2 boolean AND-1,3-di(2-pyridyl) benzene platinum chloride ((PtLCl)-Cl-1) is known to display efficient triplet luminescence in the green region of the spectrum, and to form an unusually emissive excimer that emits around 690 nm. In this contribution, the introduction of trifluoromethyl groups into either the 4- or 5-position of the pyridyl rings of the ligand is shown to lead to a red-shift in the excimer band, moving it into the near infra-red (NIR) region. The new ligands, synthesised by either Suzuki or Stille cross-coupling methods, are 1,3-bis(4-(trifluoromethyl) pyridin-2-yl)benzene HL27, 1,3-bis(4-(trifluoromethyl) pyridin-2-yl)-4,6-difluorobenzene HL28, and 1,3-bis(5-(trifluoromethyl) pyridin-2-yl)-4,6- difluorobenzene HL29, from which the corresponding Pt(II) complexes (PtLCl)-Cl-n have been prepared. The monomer and excimer emission energies in solution are compared with those of (PtLCl)-Cl-1 and (PtLCl)-Cl-22 {HL22 = 1,3-di(2-pyridyl)-4,6-difluorobenzene}. The order for the monomer can be rationalised in terms of the stabilising effects of the F atoms and the CF3 groups on the HOMO and LUMO respectively. The order of excimer emission proves to be subtly different, but the most red-shifted complex in both cases is (PtLCl)-Cl-27. The electroluminescence of neat films of the complexes as emitting layers in OLEDs displays uniquely excimer-like emission, extending well into the technologically important NIR region.