title: 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.
abstract: 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.
authors.affiliation: Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan.
authors.forename: Bo-Sian
authors.initials: BS
authors.lastname: Du
authors.forename: Chen-Huey
authors.initials: CH
authors.lastname: Lin
authors.forename: Yun
authors.initials: Y
authors.lastname: Chi
authors.forename: Jui-Yi
authors.initials: JY
authors.lastname: Hung
authors.forename: Min-Wen
authors.initials: MW
authors.lastname: Chung
authors.forename: Tsung-Yi
authors.initials: TY
authors.lastname: Lin
authors.forename: Gene-Hsiang
authors.initials: GH
authors.lastname: Lee
authors.forename: Ken-Tsung
authors.initials: KT
authors.lastname: Wong
authors.forename: Pi-Tai
authors.initials: PT
authors.lastname: Chou
authors.forename: Wen-Yi
authors.initials: WY
authors.lastname: Hung
authors.forename: Hao-Chih
authors.initials: HC
authors.lastname: Chiu
mesh_terms: D018360:Crystallography, X-Ray; D007495:Iridium / Q000737:chemistry*; D008027:Light; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D010777:Photochemistry; D013237:Stereoisomerism
chemical_list: D009281:Naphthalenes; D009942:Organometallic Compounds; D010720:Phosphines; C554882:diphenyl(1-naphthyl)phosphine; D007495:Iridium