Diphenyl(1-naphthyl)phosphine Ancillary for Assembling of Red and Orange-Emitting Ir(III) Based Phosphors; Strategic Synthesis, Photophysics, and Organic Light-Emitting Diode Fabrication
| Autor: | Min-Wen Chung, Tsung-Yi Lin, Ken-Tsung Wong, Chen-Huey Lin, Hao-Chih Chiu, Wen-Yi Hung, Gene-Hsiang Lee, Pi-Tai Chou, Jui-Yi Hung, Bo-Sian Du, Yun Chi |
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| Rok vydání: | 2010 |
| Předmět: |
Models
Molecular Light Phosphines Photochemistry Molecular Dynamics Simulation Naphthalenes Crystallography X-Ray Iridium Medicinal chemistry Chloride Adduct Inorganic Chemistry chemistry.chemical_compound Decalin Organometallic Compounds medicine Quinazoline Physical and Theoretical Chemistry Isoquinoline Molecular Structure Stereoisomerism chemistry Reagent Single crystal Phosphine medicine.drug |
| Zdroj: | Inorganic Chemistry. 49:8713-8723 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic100935b |
| Popis: | Treatment of a series of dinuclear Ir(III) complexes [(fnazo)(2)Ir(μ-Cl](2), [(fpiq)(2)Ir(μ-Cl](2), and [(fppy)(2)Ir(μ-Cl](2) with diphenyl(1-naphthyl)phosphine (dpnH) in decalin at 100 °C afforded the simple adducts, trans-N,N'-[(fnazo)(2)Ir(dpnH)Cl] (1a), trans-N,N'-[(fpiq)(2)Ir(dpnH)Cl] (1b), and trans-N,N'-[(fppy)(2)Ir(dpnH)Cl] (1c), for which the C(∧)N cyclometalating reagents, that is, fnazoH, fpiqH and fppyH, stands for 4-(4-fluorophenyl)quinazoline, 1-(4-fluorophenyl)isoquinoline and 4-fluorophenylpyridine, respectively. Single crystal X-ray diffraction study on 1a revealed existence of two trans-N,N' cyclometalates, with both chloride and dpnH donors located at the positions opposite to the phenyl substituents. Subsequent heating of 1a-1c at higher temperature afforded the second isomer (2a-2c), showing formation of cis-N,N' orientation for the aforementioned cyclometalates. Further thermolysis of either trans or cis-Ir(III) complexes 1 or 2 in presence of sodium acetate, which serves as both activator and chloride scavenger, gave successful isolation of a mixture of two fully cyclometalated Ir(III) complexes trans-N,N'-[(C(∧)N)(2)Ir(dpn)] (3a-3c) and cis-N,N'-[(C(∧)N)(2)Ir(dpn)] (4a-4c). Structural and photophysical properties of complexes 3a-3c and 4a-4c were measured and compared. Time-dependent density functional theory (DFT) studies suggested that, upon changing the C(∧)N cyclometalates from quinazolinyl, isoquinolinyl, and, finally, to pyridyl fragment, the lowest unoccupied molecular orbitals (LUMOs) are gradually shifted from the cyclometalating nitrogen heterocycles to the 1-naphthyl group of the phosphine chelate and, concomitantly altered the photophysical properties. An organic light-emitting diode (OLED) using orange-red phosphors 4a and 4b has been successfully fabricated. At the practical brightness of 500 cd·m(-2), decent external quantum efficiency of 10.6% and 12.5% could be reached for 4a and 4b, respectively, revealing the usefulness of relevant molecular architecture in designing triplet OLED emitters. |
| Databáze: | OpenAIRE |
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