Journal
INORGANIC CHEMISTRY
Volume 55, Issue 5, Pages 2299-2308Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b02691
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Funding
- University of Houston
- Welch Foundation [E-1887]
- ACS Petroleum Research Fund [54907-DNI3]
- Robert A Welch Foundation [E-1728]
- National Science Foundation [ECCS-1240510]
- Directorate For Engineering
- Div Of Electrical, Commun & Cyber Sys [1150584] Funding Source: National Science Foundation
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Cyclometalated iridium complexes with efficient phosphorescence and good electrochemical stability are important candidates for optoelectronic devices. Isocyanide ligands are strong-field ligands: when attached to transition metals, they impart larger HOMO-LUMO energy gaps, engender higher oxidative stability at the metal center, and support rugged organometallic complexes. Aryl isocyanides offer more versatile steric and electronic control by selective substitution at the aryl ring periphery. Despite a few reports of alkyl isocyanide of cyclometalated iridium(III), detailed studies on analogous aryl isocyanide complexes are scant. We report the synthesis, photophysical properties, and electrochemical properties of 11 new luminescent cationic biscyclometalated bis(aryl isocyanide)iridium(III) complexes. Three different aryl isocyanides-2,6-dimethylphenyl isocyanide (CNArdmp), 2,6-diisopropylphenyl isocyanide (CNArdipp), and 2-naphthyl isocyanide (CNArnap)-were combined with four cyclometalating ligands with differential pi-pi* energies-2-phenylpyridine (ppy), 2,4-difluorophenylpyridine (F(2)ppy), 2-benzothienylpyridine (btp), and 2-phenylbenzothiazole (bt). Five of them were crystallographically characterized. All new complexes show wide redox windows, with reduction potentials falling in a narrow range of -2.02 to -2.37 V and oxidation potentials spanning a wider range of 0.97-1.48 V. Efficient structured emission spans from the blue region for [(F(2)ppy)(2)Ir(CNAr)(2)]PF6 to the orange region for [(btp)(2)Ir(CNAr)(2)]PF6, demonstrating that isocyanide ligands can support redox-stable luminescent complexes with a range of emission colors. Emission quantum yields were generally high, reaching a maximum of 0.37 for two complexes, whereas btp-ligated complexes had quantum yields below 1%. The structure of the CNAr ligand has a minimal effect on the photophysical properties, which are shown to arise from ligand-centered excited states with very little contribution from metal-to-ligand charge transfer in most cases.
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