Rigid
naphthalene benzimidazole (NBI) based ligands (L1 and L2) are synthesized and utilized to make deep red
phosphorescent cyclometalated iridium(III) complexes ([Ir(NBI)2(PyPzCF3)] (1) and [Ir(DPANBI)2(PyPzCF3)] (2)). Complexes 1 and 2 are prepared from the reaction of L1/L2 with the aid of ancillary ligands (PyPzCF3
, 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridine)
in a two step method. The complexes are characterized by analytical
and spectroscopic methods, as well as X-ray diffraction for 1. These complexes show a strong emission in the range of
635–700 nm that extends up to the near-infrared region (800
nm). The introduction of the diphenylamino (DPA) donor group on the
naphthalene unit leads to a further red-shift in the emission. The
complexes exhibit radiative quantum efficiency (ΦPL) of 0.27–0.29 in poly(methylmethacrylate) film and relatively
short phosphorescence decay lifetimes (τ = 1.1–3.5 μs).
The structural, electronic, and optical properties are investigated
with the support of density functional theory (DFT) and time-dependent-DFT
calculations. The calculation results indicate that the lowest-lying
triplet (T1) excited state of 1 has a mixed
metal-to-ligand charge transfer (3MLCT) and ligand-centered
(3LC) character, while 2 shows a dominant 3LC character. Deep red-emitting organic light-emitting diodes
fabricated using 1 as a dopant display a maximum external
quantum efficiency of 10.9% with the CIE color coordinates of (0.690,
0.294), with an emission centered at 644 and 700 nm. Similarly, the
emitter 2 also shows a maximum external quantum efficiency
of 6.9% with emissions at 657 and 722 nm.