The development of highly efficient cyclometalated phosphorescent iridium(III) complexes is greatly promoted by their rational molecular design. Manipulating the excited states of iridophosphors could endow them with appealing photophysical properties, which play vital roles in triplet state-related photofunctional applications (e.g., electroluminescence, photodynamic therapy, etc.). In general, the most effective approach for decreasing the emission energies of iridophosphors is to extend the π-skeleton of ligands. However, the π-extension strategy often results in decreased solubility, lower synthetic yield, decreased photoluminescence quantum yield, and so forth. In this work, a simple yet efficient strategy is proposed for the effective excited-state manipulation of 2-phenyllepidine-based iridophosphors. Surprisingly, dramatic tuning of phosphorescence wavelength (∼70 nm) is achieved by simply controlling the position of a single methoxyl substituent on these iridophosphors. An oxygen-responsive iridophosphor featuring far-red emission (660 nm), long emission lifetime (1.60 μs), and high singlet oxygen quantum yield (0.73) is employed to realize accurate oxygen sensing in vitro and in vivo, and it also shows efficient photodynamic therapy in cancer cells, making it a promising candidate for the efficient image-guided photodynamic therapeutic agent. This molecular design strategy clearly demonstrates the advantages of designing novel longwavelength emissive iridophosphors without increasing the π-conjugation of the ligand.

The exploration of efficient yellow emitters featuring broad emission band plays an essential role for the complementary‐color‐based white organic light‐emitting devices (OLEDs). Herein, two new yellow ionic iridium(III) complexes (Ir1 and Ir2) having excellent sublimation ability are designed and prepared by the incorporation of chlorine‐modified 2‐phenylquinoline ligand and introduction of bulky counter ion. At room temperature, these ionic iridium(III) complexes show bright yellow phosphorescence in both solid and solution states due to the presence of bulky counter ion. They share the same emission wavelength (538 and 573 nm as the emission shoulder) with extremely high quantum yields (as high as 0.91) in Ar‐saturated CH2Cl2. Notably, those complexes also exhibit very broad full width at half maximum (FWHM) (up to 100 nm) attributed to almost the same intensities of emission maximum and shoulder, making them excellent candidates for white electroluminescence. The as‐prepared yellow OLEDs show high external quantum efficiency (EQE) of 11.6% and broad FWHM of 105 nm. The two‐color‐based white OLED is prepared with peak EQE of 9.2%, the 1931 CIE coordinate of (0.29, 0.31), and color rendering index of 79, proving that these new ionic iridium(III) complexes show a great potential for white electroluminescence.

The excited-state manipulation of the phosphorescent iridium(III) complexes plays a vital role in their photofunctional applications. The development of the molecular design strategy promotes the creative findings of novel iridium(III) complexes. The current molecular design strategies for iridium(III) complexes mainly depend on the selective cyclometalation of the ligands with the iridium(III) ion, which is governed by the steric hindrance of the ligand during the cyclometalation. Herein, a new molecular design strategy (i.e., random cyclometalation strategy) is proposed for the effective excited-state manipulation of phosphorescent cyclometalated iridium(III) complexes. Two series of new and separable methoxyl-functionalized isomeric iridium(III) complexes are accessed by a one-pot synthesis via random cyclometalation, resulting in a dramatic tuning of the phosphorescence peak wavelength (∼57 nm) and electrochemical properties attributed to the high sensitivity of their excited states to the position of the methoxyl group. These iridium(III) complexes show intense phosphorescence ranging from the yellow (567 nm) to the deep-red (634 nm) color with high photoluminescence quantum yields of up to 0.99. Two deep-red emissive iridium(III) complexes with short decay lifetimes are further utilized as triplet emitters to afford efficient solution-processed electroluminescence with reduced efficiency roll-offs.