Theoretical investigation on the photophysical properties of N‐heterocyclic carbene iridium (III) complexes (fpmb)xIr(bptz)3‐x (x = 1−2)

In the search for efficiently phosphorescent materials, this article presents a rational design and theoretical comparative study of some photophysical properties in the (fpmb)xIr(bptz)3‐x (x = 1–2), which involve the usage of two 2‐pyridyl triazolate (bptz) chromophores and a strong‐field ligand fpmb (fpmb = 1‐(4‐difluorobenzyl)‐3‐methylbenzimidazolium). The first principle theoretical analysis under the framework of the time‐dependent density functional theory approach is implemented in this article to investigate the electronic structures, absorption and phosphorescence spectra. It is intriguing to note that 1 and 2 exhibit theirs blue phosphorescent emissions with maxima at 504 and 516 nm, respectively. Furthermore, to obtain the mechanism of low phosphorescence yield in 1 and estimate the radiative rate constant kr for 2, we approximately measure the radiative rate constant kr, the spin‐orbital coupling (SOC) value, ΔE (S − T), and the square of the SOC matrix element (2) for 1 and 2. Finally, we tentatively come to conclusion that the switch of the cyclometalated ligand from the main to ancillary chelate seems to lower the splitting ΔE (S − T) in the current system. © 2012 Wiley Periodicals, Inc. J Comput Chem, 2012