Cyclometalated Iridium(III) Complexes Incorporating Aromatic Phosphonate Ligands: Syntheses, Structures, and Tunable Optical Properties

[Image: see text] The incorporation of phosphonate ligands into the cyclometalated iridium(III) complexes can not only tune their electronic and optical properties but also provide the possibility of anchoring these molecules on the semiconductor surfaces for further applications. Herein, we report the first examples of mononuclear cyclometallated iridium(III) complexes incorporating phosphonate ligands, namely, [Ir(ppy)(2)(HL(1))]·0.5H(2)O (1), [Ir(ppy)(2)(HL(2))]·0.5H(2)O (2), [Ir(dfppy)(2)(HL(1))] (3), and [Ir(dfppy)(2)(HL(2))]·3.5H(2)O (4) (ppy = 2-phenylpyridine, dfppy = 2-(2,4-difluorophenyl)pyridine, H(2)L(1) = 2-pyridylphosphonic acid, H(2)L(2) = 2-quinolinephosphonic acid). Luminescent spectra are studied both in solution and in the solid state, and significantly red-shifted broad emission bands are observed in complexes 2 and 4. The experimental and density functional theory (DFT) time-dependent-DFT calculation results indicate that the expansion of the aromatic conjugation length in the ancillary phosphonate ligands decreases the lowest unoccupied molecular orbital energy levels of the systems, originating from the triplet state associated with the ancillary ligand such as (3)MLCT, (3)LC, and (3)LLCT charge-transfer transitions.