Example 1
μ-Dichloro Dimer D1:
3.50 g (11.5 mmol) of 1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole L1 are initially charged in 200 ml of 2-ethoxyethanol/water (ratio 3/1) and admixed with 1.84 g (5.2 mmol) of iridium(III) chloride trihydrate. The reaction mixture is heated at reflux for 18 h. After cooling, 50 ml of distilled water are added. The precipitate is filtered off, washed with distilled water and dried. This gives 3.50 g (80%) of p-dichloro dimer D1 as a yellow powder.
1H NMR (CD2Cl2, 400 MHz):
δ=0.95 (d, 3JH,H=6.9 Hz, 12H), 1.18 (d, 3JH,H=6.9 Hz, 12H), 1.27 (d, 3JH,H=6.9 Hz, 12H), 1.34 (d, 3JH,H=6.9 Hz, 12H), 2.80-2.91 (m, 8H), 6.08 (d, 3JH,H=7.7 Hz, 4H), 6.24 (d, 3JH,H=7.7 Hz, 4H), 6.39 (pt, 3JH,H=7.5 Hz, 4H), 6.53 (pt, 3JH,H=7.5 Hz, 4H),6.97 (d, JH,H=1.5 Hz, 4H), 7.39-7.45 (m, 8H), 7.59 (t, 3JH,H=7.8 Hz, 4H), 7.67 (d, JH,H=1.5 Hz, 4H).
Complex Em1-s:
2.37 g (7.2 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 are heated to 90° C. under reduced pressure for 18 h. After cooling to room temperature, first 100 ml of anhydrous toluene and then a suspension of 3.00 g (1.8 mmol) of chloro dimer D1 and 150 ml of anhydrous toluene are added. The mixture is heated to 90° C. for 2 h. The white precipitate formed (1.15 g, imidazolium chloride C1*) is filtered off. The filtrate is washed with 3×40 ml of saturated NaHCO3 solution and 1×40 ml of distilled water, dried over MgSO4 and freed of the solvent under reduced pressure. The residue is washed with 2×50 ml of methanol, recrystallized from methylene chloride/methanol and then recrystallized from nitromethane. This gives 3.2 g of the complex Em1-s as a yellow powder (82%).
Em1-s: The configuration of Em1-s corresponds to the configuration of the pseudo-meridional isomer S1a or S1b. Em1-s is present as the racemate; for crystal structure see
1H NMR (CD2Cl2, 400 MHz):
δ=0.88 (d, 3JH,H=6.8 Hz, 3H), 0.91 (d, 3JH,H=6.9 Hz, 9H), 1.14 (d, 3JH,H=6.9 Hz, 3H), 1.16 (d, 3JH,H=6.8 Hz, 3H), 1.20 (d, 3JH,H=6.9 Hz, 3H), 1.28 (d, 3JH,H=6.9 Hz, 3H), 2.08 (sept, 3JH,H=6.7 Hz, 1H), 2.65-2.77 (m, 3H), 6.08-6.15 (m, 3H), 6.19-6.25 (m, 2H), 6.42-6.45 (m, 1H), 6.50-6.52 (m, 2H), 6.67 (s, b, 2H), 6.71 (dt, 3JH,H=7.4 Hz, J=1.2 Hz, 1H), 6.75 (d, J=1.5 Hz, 1H), 6.79-6.87 (m, 6H), 7.00-7.07 (m, 2H), 7.28-7.43 (m, 9H), 7.50 (t, 3JH,H=7.8 Hz, 1H), 7.56 (t, 3JH,H=7.8 Hz, 1H), 7.71 (d, 3JH,H=7.5 Hz, 1H).
Photoluminescence (in a film, 2% in PMMA):
λ=460, 490 nm, CIE: (0.19; 0.34)
Example 17
Production of an OLED—Comparison of Different Emitters
The ITO substrate used as the anode is cleaned first with commercial detergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection properties of the ITO. Next, the hole injection layer AJ20-1000 from Plexcore respectively PEDT: PSS (CLEVIOS P AR 4083) from H. C. Starck Is spun on from solution.
Thereafter, the organic materials specified below are applied by vapor deposition to the cleaned substrate at about 10−7-10−9 mbar at a rate of approx. 0.5-5 nm/min. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC)3 with a thickness of 45 nm, of which the first 35 nm are doped with MoOx to improve the conductivity,
(for preparation see Ir complex (7) in the application PCT/EP/04/09269).
Subsequently, a mixture of emitter and of the compound Ma1 is applied by vapor deposition with a thickness of 40 nm, the latter compound functioning as a matrix material. Subsequently, the material Ma1 is applied by vapor deposition with a thickness of 10 nm as an exciton and hole blocker.
Next, an electron transporter BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapor deposition in a thickness of 20 nm, as are a 0.75 nm-thick lithium fluoride layer and finally a 100 nm-thick Al electrode. All components are adhesive-bonded to a glass lid in an inert nitrogen atmosphere.
To characterize the OLED, electroluminescence spectra are recorded at different currents and voltages. In addition, the current-voltage characteristic is measured in combination with the light output emitted. The light output can be converted to photometric parameters by calibration with a photometer. The lifetime t1/2 of the diode is defined by the time taken for the luminance to fall to 50% of its initial value. The lifetime measurement is carried out at a constant current.
For the different emitters in the above-described OLED structure, the following electrooptical data are obtained:
Example 19
Influence of a Mixed Electron Conductor Layer
The example which follows shows the influence of the doping of the BCP electron conductor layer with Liq.
The following OLED structure is used:
ITO—40 nm AJ20—1000—35 nm Ir(DPBIC)3 mixed with MoOx—10 nm Ir(DPBIC)3—40 nm Ma1 mixed with 20 wt % Em1-i—5 nm Ma1—40 nm electron conductor—1 nm Liq-100 nm Al. The preparation of the OLED is carried out in analogy to Example 17.
Example 20
Complex Em9-s:
Imidazoliumiodide C6 corresponds to a pre-intermediate of the compound “example 1” in WO 2006056418. The synthesis is carried out in analogy to the synthesis of the compound “example 1” in WO 2006056418.
2.0 g (6.4 mmol) of imidazoliumiodide C6 and 0.75 g (3.2 mmol) Ag2O are stirred in 170 ml anhydrous acetonitrile for 4 h at 50° C. The solvent is then removed in vacuo.
To the residue 170 ml anhydrous toluene is added and 3.6 g (2.1 mmol) chlorodimer D1 are added. Subsequently it is heated under reflux for 24 h. After cooling the reaction mixture is filtered. The filtrate is freed from solvent in vacuo. To the residue methylene chloride is added, washed with water, reduced after drying and purified by chromatography (cyclohexane/acetic ester), where by 0.26 g Em9-s are isolated (6%) and 0.63 g of a mixed fraction of complex Em9-s with not complexed phenylimidazol-ligand as well as 0.10 mg of a further complex with inverse ligand stoichiometry. Further 1.3 g of chlorodimer D1 (36%) are reisolated.
1H-NMR (CD2Cl2, 400 MHz):
δ=0.83 (d, 3H), 0.89-0.96 (m, probably interpreted as 4×d, 12H), 1.00 (d, 3H), 1.13 (d, 3H), 1.15 (d, 3H), 1.98 (sept, 1H), 2.31 (sept, 1H), 2.70 (sept, 1H), 2.74 (sept, 1H), 3.21 (s, 3H), 6.10 (dd, 2H), 6.37-6.45 (m, 4H), 6.56-6.65 (m, 4H), 6.70 (dd, 1H), 6.83 (me, 1H), 6.95 (d, 1H), 7.06 (me, 1H), 7.19 (me, 2H), 7.25-7.31 (m, 4H), 7.44-7.50 (m, 3H).
MS (Maldi):
m/e=979 (M+H)+
photoluminescence (in film, 2% in PMMA):
λmax=456, 487 nm, CIE: (0.20; 0.30)
Example 24
Diode Structure:
ITO—PEDT:PSS—35 nm Ir(DPBIC)3 mixed with 10 wt.-% MoOx—10 nm Ir(DPBIC)3—40 nm Matrix MaX mixed with 15 wt.-% Em1-s-10 nm LB1—20 nm electron conductor BCP—0.70 nm LIF—100 nm Al.
The preparation of the diode is carried out in analogy to Example 17.
Exciton and hole blocker LB1:
Structures of the matrices “MaX” (=Ma2−Ma6) and description of their synthesys in WO2010/079051:
Example 25
Structure A: ITO—AJ20—1000—35 nm Ir(DPBIC)3 mixed with 50 wt.-% MoO3—10 nm Ir(DPBIC)3—40 nm “MaX” mixed with 20 wt.-% Em1-i—5 nm “MaX”—40 nm electron conductor BCP: Liq 50 wt.-%—1 nm Liq-100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
Structure B: ITO—AJ20—1000—35 nm Ir(DPBIC)3 mixed with 10 wt.-% MoO3—10 nm Ir(DPBIC)3—40 nm “MaX” mixed with 15 wt.-% Em1-i—10 nm LB1—20 nm electron conductor BCP—0.70 nm LiF—100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
Structures of the Matrices MaX and Description of their Synthesis in WO2010/079051:
Example 26
ITO—AJ20—1000-10 nm Mal mixed with 10 wt.-% MoOx—10 nm Ma10 mixed with 15 wt.-% Em1-i and 15 wt.-% Ma1—5 nm Ma1—20 nm electron conductor BCP mixed with 20 wt.-% Ma1—1 nm Cs2CO3— 100 nm Al. The preparation of the diode is carried out in analogy to Example 17.
The synthesis of matrix material Ma10 is described in JP2009046408, compound B, [0039], p. 13.
Ma10
