title: Tris-cyclometalated iridium(III) complexes of carbazole(fluorenyl)pyridine ligands: synthesis, redox and photophysical properties, and electrophosphorescent light-emitting diodes.
abstract: Using ligands synthesized by Suzuki cross-coupling methodology, new phosphorescent homoleptic tris-cyclometalated complexes have been obtained, namely fac-[Ir(Cz-2-Fl(n)Py)(3)] (1 d-f) and fac-[Ir(Cz-3-Fl(n)Py)(3)] (2 d-f), which are solution-processible triplet emitters (Cz denotes N-hexylcarbazole, n is the number of 9,9'-dihexylfluorene (Fl) units (n=0,1,2) and Py is pyridine). In all cases, Py and Fl are substituted at the 2- and 2,7-positions, respectively, and Cz moieties are substituted by either Py or Fl at the 2- or 3-positions, in series 1 and 2, respectively. The oxidation potential of 1 d studied by cyclic voltammetry ({E{{{\rm ox}\hfill \atop 1/2\hfill}}}=0.14 V, versus Ag/AgNO(3), CH(2)Cl(2)) is less positive (i.e. raised HOMO level) compared to that of the isomer 2 d ({E{{{\rm ox}\hfill \atop 1/2\hfill}}}=0.30 V), where the Cz-nitrogen is meta to the Ir center. Ligand-centered oxidations occur at more positive potentials, leading to 7+ oxidation states with good chemical reversibility and electrochemical quasi-reversibility, for example, for 2 f {E{{{\rm ox}\hfill \atop {\rm pa}\hfill}}} =0.45 (1e), 0.95 (3e), 1.24 V (3e). Striking differences are seen in the solution-state photophysical data between complexes [Ir(Cz-2-Py)(3)] (1 d) and [Ir(Cz-3-Py)(3)] (2 d), in which the Cz moiety is bonded directly to the metal center: for the latter there is an 85 nm blue-shift in emission, a decrease in the luminescence lifetime and an increase in the PLQY value. Organic light emitting devices were made by spin-coating using polyspirobifluorene:bis(triphenyl)diamine (PSBF:TAD) copolymer as host and the complexes 1 d or 2 d as dopants. Turn-on voltages are low (3-4 V). With 1 d orange light is emitted at lambda(max)=590 nm with an EQE of 1.3 % (at 7.5 mA cm(-2)) and an emission intensity (luminance) of 4354 cd m(-2) (at 267 mA m(-2)). The green emission from 2 d devices (lambda(max)=500 nm) is due to the reduced electron-donating ability of the carbazole unit in 2 d. Recording the EL spectra of the 1 d device at 6 V (current density, 100 mA cm(-2)) established that the time to half brightness was about 9 h under continuous operation with no change in the spectral profile, confirming the high chemical stability of the complex.
authors.affiliation: Department of Chemistry, Durham University, Durham DH1 3LE, UK.
authors.forename: Sylvia
authors.initials: S
authors.lastname: Bettington
authors.forename: Mustafa
authors.initials: M
authors.lastname: Tavasli
authors.forename: Martin R
authors.initials: MR
authors.lastname: Bryce
authors.forename: Andrew
authors.initials: A
authors.lastname: Beeby
authors.forename: Hameed
authors.initials: H
authors.lastname: Al-Attar
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Monkman