KR20050016502A - Phosphorescent and Luminescent Conjugated Polymers and Their Use in Electroluminescent Assemblies - Google Patents

Abstract

The present invention relates to phosphorescent or luminescent conjugated polymers which emit from the phosphorescence of covalently bonded metal complexes, optionally with fluorescence of the polymer chain. The present invention also relates to a process for the preparation of said polymers and to their use in electroluminescent assemblies.

Description

Phosphorescent and Luminescent Conjugated Polymers and Their Use in Electroluminescent Assemblies}

All molar weights mentioned below were determined by GPC (gel permeation chromatography) (assayed in polystyrene standards, dichloromethane solvent).

Iridium precursor complex used:

Example 1 Repetition of Formulas A and BI-1 (Ar ¹ = 2,7- (9,9-di-n-octyl) fluorenyl, R ² = octyl, L = 2-phenylpyridine (ppy)) Synthesis of Polymers with Units

(Ppy) ₂ Ir (μ-Cl) ₂ Ir (ppy) ₂ (67 mg) and silver trifluoromethanesulfonate (32.1 mg) in dichloromethane (25 mL) / acetonitrile (1.25 mL) under dark under nitrogen Stirred at reflux for 10.5 h. The silver chloride formed was separated by filtration, the solvent was distilled off, and then the ligand polymer poly-[(9,9'-di-) dissolved in a mixture of anisole and 2-ethoxyethanol (85:15) (25 mL). n-octyl-2,7-fluorenyl) -co- (2,5-pyridyl)] (number of units A: number of units BI-1 = 12: 1; M _w = 88,100 (D = 2.82) 200 mg) was added. The solution was stirred at reflux for 23 h under nitrogen. The solution was filtered and evaporated to 13 ml, then the polymer was precipitated in 400 ml of methanol. Then 195.6 mg of the desired phosphorescent polymer was obtained as orange fibrous product after Soxhlet extraction with methanol / acetone (1: 1) and vacuum drying. ¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ = 9.09 (H _ppy ), 8.58 (H _ppy ), 8.26 (H _ppy ), 7.9-7.6 (H _polyfluorene + H _ppy ), 6.94 (H _ppy ), 6.48 (H _ppy ), 2.12 (H _{CH 2} ), 1.14 (H _{CH 2} ), 0.82 (H _{CH 3} ); Photoluminescence (thin layer on quartz glass substrate, λ _ex = 296 nm); λ _{em, max} = 630 nm.

The synthesis of other phosphorescent polymers having repeating units of formula A and B-I-1 or A and B-I-2 could be done in a similar manner.

Example 2-a: Formula C-1 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = hexyl, L = 2-benzo [b] thiophene- Synthesis of Polymers of 2-yl-pyridine (bthpy)

End group-functionalized (salicyaldehyde-n-hexylimine) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 8,400 (D = 2.1); 400 mg) , (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (65 mg) and sodium carbonate (14 mg) in a mixture of 1,2-dichloroethane (50 mL) and ethanol (10 mL) under a nitrogen atmosphere. Heated to reflux for 40 hours. After cooling, chloroform (40 mL) was added and filtration was performed. The filtrate was concentrated and chromatographed on silica gel (CH ₂ Cl ₂ ). The product fractions were combined and concentrated (5 mL) and the product precipitated in methanol (300 mL). After drying in vacuo, 366 mg of the desired product were obtained as a yellow-orange aggregated solid giving a strong red luminescence under a UV lamp. ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 8.89 (d), 8.47 (d), 8.17 (s), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.53 (m), 7.35 ( m), 7.05 (m), 6.92 (t), 6.81 (m), 6.37 (d), 6.09 (d), 3.15 (br, H _{N-CH 2} ), 2.12 (m, H _{CH 2, polyfluorene} ), 1.14 (br, H _{CH 2, polyfluorene} ), 0.82 (t, H _{CH 3, polyfluorene} ); GPC (CH ₂ Cl ₂ ): M _w = 10,500; Photoluminescence (thin layer on quartz glass substrate, λ _ex = 372 nm), λ _{em, max} = 612 nm; Electroluminescence: λ _{em, max} = 612 nm.

Example 2-b: Formula C-1 (Ar ¹ ₌ 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = Hexyl, L = synthesis of polymer of 2-benzo [b] thiophen-2-yl-pyridine (bthpy)

The procedure was similar to Example 2-a, but with end group-functionalization (salicyaldehyde-n-hexylimine) poly-2,7- (9,9'-di-n-octyl) fluorene (M _w = 35,200 (D = 3.4); 700 mg), (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (40 mg), Na ₂ CO ₃ (8.5 mg), 1,2-dichloroethane (50 mL ) And ethanol (10 mL) were used. The reaction time was 32 hours. After the product was isolated, 603 mg of a yellow-orange fibrous solid was obtained which gave a strong red emission under UV lamp.

Example 3: Formula C-1 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = Hexyl, L = synthesis of polymer of 2- (2-thienyl) pyridine (thpy)

End group-functionalized (salicyaldehyde-n-hexylimine) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 8,400 (D = 2.1); 400 mg) , (thpy) ₂ Ir (μ-Cl) ₂ Ir (thpy) ₂ (55 mg) and sodium carbonate (14 mg) in a mixture of 1,2-dichloroethane (50 mL) and ethanol (10 mL) under nitrogen atmosphere. Heated to reflux for 27 hours. After cooling, chloroform (40 mL) was added and filtration was performed. The filtrate was concentrated and chromatographed on silica gel (CH ₂ Cl ₂ ). The product fractions were combined and concentrated (4 mL) and the product precipitated in methanol (300 mL). After drying in vacuo, 332 mg of the desired product were obtained as a yellow-orange aggregated solid that gave a slight orange luminescence under a UV lamp. ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 8.99 (d), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.53 (m), 7.35 (m), 7.05 (d), 6.62 ( m), 5.91 (d), 3.75 (br, H _{N-CH 2} ), 2.12 (m, H _{CH 2, polyfluorene} ), 1.14 (br, H _{CH 2, polyfluorene} ), 0.82 (t, H _{CH 3, poly Fluorene} ).

Example 4: Formula C-1 (Ar ¹ ₌ 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = Hexyl, L = 2-phenyl-benzothiazole (btz))

End group-functionalized (salicyaldehyde-n-hexylimine) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 8,400 (D = 2.1); 250 mg) , (btz) ₂ Ir (μ-Cl) ₂ Ir (btz) ₂ (39 mg) and sodium carbonate (10 mg) in a mixture of 1,2-dichloroethane (30 mL) and ethanol (6 mL) under a nitrogen atmosphere. Heated to reflux for 36 hours. After cooling, chloroform (40 mL) was added and filtration was performed. The filtrate was concentrated and chromatographed on silica gel (CH ₂ Cl ₂ ). The product fractions were combined and concentrated (10 mL) and the product precipitated in methanol (500 mL). After drying in vacuo, 180 mg of the desired product were obtained as an orange solid giving a strong orange emission under UV lamp (366 nm). ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 8.75 (d), 8.63 (d), 8.03 (s), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.5-7.3 (m), 6.87 (m), 6.73 (m), 6.62 (m), 6.41 (t), 6.26 (d), 5.99 (d), 3.48, 3.28 (br, H _N-CH2 ), 2.12 (m, H _{CH2, poly Fluorene} ), 1.14 (br, H _{CH 2, polyfluorene} ), 0.82 (t, H _{CH 3, polyfluorene} ). Photoluminescence (thin layer on quartz glass substrate, λ _ex = 452 nm): λ _{em, max} = 581, 614 (sh) nm; Electroluminescent lambda _{em, max} = 570 (sh), 612 nm.

Example 5: Formulas A and BI-6 (Ar ¹ = 2,7- (9,9'-di-2-ethylhexyl) fluorenyl, R ⁴ = hexyl, L = 2-benzo [b] thiophen-2-yl- (5-trifluoromethyl) pyridine (bthpy-cf3)) Synthesis of red-phosphorescent polymers with repeat units

2,7- (9,9'-di-2-ethylhexyl) fluorene unit A and 3,5-crosslinked uncomplexed salicylic-N-hexylimine unit BI-6 were converted to 98.5 (A): 1.5 (BI Random polyfluorene ligand copolymer (M _w = 53,900 (D = 2.15)) (250 mg), (bthpy-cf3) ₂ Ir (μ-Cl) ₂ Ir (bthpy-cf3) ₂ (11 mg) and sodium methanolate (0.8 mg) were heated to reflux under nitrogen atmosphere for 20 hours in a mixture of chloroform (15 mL) and methanol (1 mL). Post-treatment was performed as in Example 23, whereby 211 mg of a fibrous yellow solid was obtained under strong UV light with a deep red emission.

Complexation was demonstrated from a ¹ H NMR spectrometer.

Film emission spectroscopy: (λ _exc = 411 nm); λ _{em, max} = 640 nm.

Example 6: Formula C-2 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁵ = methyl, L = 2- (2-thienyl) pyridine (thpy Synthesis of Polymers of))

End group-functionalized (4-benzoylacetone) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 7,600 (D = 1.8); 250 mg), (thpy) ₂ Ir (μ-Cl) ₂ Ir (thpy) ₂ (65 mg) and sodium carbonate (63.6 mg) were stirred in reflux under nitrogen atmosphere for 13.5 hours in 2-ethoxyethanol (15 mL). After cooling, water (30 mL) was added, stirred and extracted with chloroform (3 x 50 mL). The extract was evaporated to dryness, taken again in chloroform and the product introduced into methanol to precipitate. After chromatography on silica gel (chloroform), the product fractions were evaporated and again precipitated in methanol. After drying in vacuo, 97.8 mg of a yellow-orange aggregated solid was obtained which gave a strong orange emission under UV lamp (366 nm). ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 8.44 (d), 8.40 (d), 8.17 (d), 8.08 (d), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.51 ( m), 7.34 (m), 6.90 (m), 6.25 (d), 6.23 (d), 5.98 (s), 2.12 (br, H _{CH 2, polyfluorene} ), 1.98 (s), 1.14 (br, H _{CH 2, polyfluorene} ), 0.82 (t, H _{CH 3, polyfluorene} ).

Example 7: Formula C-2 (Ar ¹ = 2,7- (9,9′-di-n-octyl) fluorenyl, R ⁵ = methyl, L = 2-benzo [b] -thiophene-2 Synthesis of Polymers of -yl-pyridine (bthpy)

End group-functionalized (4-benzoylacetone) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 19,500 (D = 2.3) dissolved in chloroform (22.5 mL) 300 mg) and (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (39 mg) were added dropwise to a solution of sodium methylate (2.4 mg) in methanol (0.75 mL) under nitrogen atmosphere and at room temperature. After stirring for 1 hour, the mixture was stirred for 5.5 hours under reflux. After cooling, chloroform (20 mL) was added, filtered and the filtrate was evaporated. After chromatography on silica gel (dichloromethane), the product fractions were concentrated (5 mL) and precipitated in methanol (400 mL). After drying in vacuo, 203 mg of an orange aggregate product was obtained, giving a strong red emission under UV lamp (366 nm). ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 8.53 (d), 8.48 (d), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.40-7.30 (m), 7.09 (m), 6.98 (m), 6.84 (t), 6.30 (d), 6.27 (d), 6.02 (s), 2.12 (br, H _{CH 2, polyfluorene} ), 1.96 (s), 1.14 (br, H _{CH 2, poly Fluorene} ), 0.82 (t, H _{CH3, polyfluorene} ).

Example 8: Formula C-2 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁵ = methyl, L = 4-fluorophenyl-2-pyridine (fpp Synthesis of Polymers of))

End group-functionalized (4-benzoylacetone) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 19,500 (D = 2.3) dissolved in chloroform (15 mL) 200 mg) and (fpp) ₂ Ir (μ-Cl) ₂ Ir (fpp) ₂ (23 mg) were added dropwise to a solution of sodium methylate (1.6 mg) in methanol (0.5 mL) under nitrogen atmosphere and at room temperature. After stirring for 1 hour, the mixture was stirred for 5 hours under reflux. After cooling, it was filtered and the filtrate was evaporated to dryness. The product was again taken up in dichloromethane and chromatographed on silica gel (dichloromethane). The product fractions were concentrated and precipitated in methanol. After drying in vacuo, 192 mg of a yellow product giving blue emission under UV lamp (366 nm) was obtained. ¹ H-NMR (CDCl ₃ , 400 MHz, TMS): δ = 9.13 (d), 8.54 (d), 8.49 (d), 7.90-7.60 (H _{Ar-polyfluorene} ), 7.40-7.30 (m), 7.15 (m), 6.60 (d), 6.58 (d), 5.99 (s), 5.95 (m), 5.92 (d), 2.12 (br, H _{CH 2, polyfluorene} ), 1.97 (s), 1.14 (br , H _{CH 2, polyfluorene} ), 0.82 (t, H _{CH 3, polyfluorene} ).

Example 9

An organic light emitting diode (OLED) was prepared using the substrate according to the invention from Example 2-a. The following procedure was applied to the production of OLEDs.

1. Cleaning ITO Substrate

ITO-coated glass (Merck Balzers AG, FL, Part No. 253 674 XO) was cut into 50 mm x 50 mm pieces (substrates). Subsequently, the substrate was washed for 15 minutes in an aqueous solution of Mucasol at a concentration of 3% in an ultrasonic bath. The substrate was then rinsed with distilled water and rotary dried in a centrifuge. This rinsing and drying process was repeated 10 times.

2. Application of the Baytron® P Layer

Approximately 10 ml of a 1.3% concentration of polyethylenedioxythiophene / polysulfonic acid solution (Bayer AG, Bitelon® P, TP AI 4083) was filtered (Millipore HV, 0.45 μm). The substrate was then placed on a spin coater and the filtered solution was dispersed over the ITO-coated side of the substrate. The turntable was then rotated at 500 rpm for 3 minutes to remove the supernatant centrifugally. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The layer thickness was 60 nm (Tencor, Alphastep 200).

3. Application of emitter layer

5 ml of a 1 wt% toluene solution of the material according to the invention from Example 2-a was filtered (Millipore HV, 0.45 μm) and dispersed over a dry Bitron® P layer. The turntable was then rotated at 300 rpm for 30 seconds to remove the supernatant centrifugally. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The layer thickness was 150 nm.

4. Application of metal cathode

Metal electrodes were applied to the organic layer system by vapor deposition. The deposition apparatus (Edwards) used for this purpose was constructed in an inert gas glovebox (Braun). The substrate was placed on a perforated mask (pore diameter 2.5 mm) with the organic layer facing down. A 30 nm thick Ca layer followed by a 200 nm Ag layer was applied successively by deposition at a pressure of p = 10 ⁻³ Pa from two vaporization boats. The deposition rate was 10 s / sec for Ca and 20 s / sec for Ag.

5. Characterization of OLED

Two electrodes of the organic LED were connected to the power source via electrical leads. The positive electrode was connected to the ITO electrode and the negative electrode was connected to the metal electrode. OLED current and electroluminescent intensity were detected by photodiode (EG & G C30809E) and plotted as a function of voltage. The spectral distribution of the electroluminescence was then measured using a glass fiber spectrometer (Zeiss MSC 501). All OLED characterizations were done in a glovebox under inert conditions. At voltages above 6 volts, electroluminescence was detectable. The color of the electroluminescence was red and the maximum point of the spectrophotoluminescence distribution was voltage dependent and 612 nm (see FIG. 1). The CIE color coordinates of the emission are x = 0.660; y = 0.332.

1: Electroluminescent Spectroscopy from Example 9

Comparative Example 1

The procedure was the same as in Example 9, but for Step 3 (application of the emitter layer) it was different as follows.

3. Application of emitter layer

5 ml of a 1 wt% chloroform solution of poly-2,7- (9,9'-di-n-octyl) fluorene (see Structural Reference) was filtered (Millipore HV, 0.45 μm) and dried byteron (registered) Trademark) on the P layer. The turntable was then rotated at 2,500 rpm for 120 seconds to remove the supernatant centrifugally. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness was 250 nm.

Poly-2,7- (9,9'-di-n-octyl) fluorene

In Comparative Example 1 the color of the electroluminescence was blue, the maximum point of the spectral electroluminescence distribution was 438.5 nm (see Fig. 2), the CIE color coordinates x = 0.164; y = 0.113.

2: Electroluminescent Spectroscopy from Comparative Example 1

Compared with Example 9, it was clearly shown that the covalent linkage of the Ir complex to the polyfluorene ligand group changes the emission color.

Comparative Example 2

The procedure was the same as in Example 9, but for Step 3 (application of the emitter layer) it was different as follows.

3. Application of emitter layer

1 consisting of 97% by weight of poly-2,7- (9,9'-di-n-octyl) fluorene (see Example 8) and 3% by weight of tris (2-phenylpyridine) iridium (see formula) 5 ml of wt% chloroform solution was filtered (Millipore HV, 0.45 μm) and dispersed over a dry Bitron® P layer. The turntable was spun at 2,500 rpm for 150 seconds to remove the supernatant centrifugally. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness was 250 nm.

Tris (2-phenylpyridine) iridium

Electroluminescence spectroscopy of this structure corresponded to that described in Comparative Example 1 (see FIG. 2). In other words, the spectra were identical to those of pure poly-2,7- (9,9'-di-n-octyl) fluorene.

This example has shown that doping the polyfluorene emitter polymer with an Ir complex by simple mixing does not result in the desired release of the iridium complex.

Example 10: Formula (Ia-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = 4-fluorophenyl-2-pyridine (fpp)) synthesis of polymers

600 mg of a ligand polymer containing 4 mol% of uncomplexed salicylic-N-hexylimine end groups in a mixture of 42 ml of 1,2-dichloroethane and 8 ml of ethanol, (fpp) ₂ Ir (μ-Cl) ₂ Ir 30 mg (0.026 mmol) of (fpp) ₂ and 7.8 mg (0.074 mmol) of sodium carbonate were stirred under reflux for 38 h under a nitrogen atmosphere. After filtration, the solution was evaporated to dryness and the residue was taken up in a small amount of chloroform and chromatographed on silica gel (CH ₂ Cl ₂ ). The product fractions were concentrated (15 mL) and introduced in methanol (800 mL) to precipitate. Suction filtration and vacuum drying with oil pump gave 507 mg of product (yellow, fibrous).

The polymer contained 4 mol% end groups. That is, the iridium complex concentration was 4 mol% based on the fluorene derivative portion in the polymer.

The product gave a white luminescence under UV irradiation (366 nm).

GPC (CH ₂ Cl ₂ , based on PS): M _w = 40,100

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Example 11: Formula (Ia-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = 4-fluorophenyl-2-pyridine (fpp)) synthesis of polymers

Synthesis was as described in Example 10 and contained a ligand polymer (M _w) containing 2 mol% of uncomplexed salicylic-N-hexylimine end groups in a mixture of 15 ml of 1,2-dichloroethane and 2.8 ml of ethanol. = 71,300) 200 mg, (fpp) ₂ Ir (μ-Cl) ₂ Ir (fpp) ₂ 5 mg (0.004 mol) and sodium carbonate 1.3 mg (0.011 mmol) were used. The reaction time was 38 hours under reflux. After workup, 123 mg of product was obtained (pale yellow, fibrous).

The polymer was the same as the polymer of Example 10, but the polymer of Example 11 contained only 2 mol% of end groups. That is, the iridium complex concentration was 2 mol% based on the fluorene derivative portion in the polymer.

The product gave a white luminescence under UV irradiation (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Example 12: Formula (Ia-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = phenyl-2-pyridine (ppy)) Synthesis of Polymers

The procedure was as described in Example 10 and contained a ligand polymer (M _w) containing 2 mol% of uncomplexed salicylic-N-hexylimine end groups in a mixture of 15 ml of 1,2-dichloroethane and 3 ml of ethanol. 71 mg, (ppy) ₂ Ir (μ-Cl) ₂ Ir (ppy) ₂ 4.3 mg (0.004 mmol) and 1 mg (0.009 mmol) of sodium carbonate were used. The reaction time was 8 hours under reflux. After workup, 127 mg of product was obtained (yellow, fibrous).

The product contained 2 mol% end groups. That is, the iridium complex concentration was 2 mol% based on the fluorene derivative portion in the polymer.

The product gave a white luminescence under UV irradiation (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Film emission spectroscopy (λ _exc = 398 nm): λ _em = 439, 465, 550 nm.

Example 13: Formula (Ia-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = phenyl-2-pyridine (ppy)) Synthesis of Polymers

The procedure was as described in Example 12, with a ligand polymer containing 1 mol% of uncomplexed salicylic-N-hexylimine end groups in a mixture of 25 ml of 1,2-dichloroethane and 4 ml of ethanol (M _w = 122,600) 350 mg, (ppy) ₂ Ir (μ-Cl) ₂ Ir (ppy) ₂ 8.6 mg (0.008 mmol) and 2.2 mg (0.02 mmol) sodium carbonate were used. The reaction time was 18.5 hours under reflux. After workup, 284 mg of product was obtained (pale yellow, fibrous).

The polymer was the same as the polymer of Example 12, but the polymer of Example 13 contained only 1 mol% of end groups. That is, the iridium complex concentration was 1 mol% based on the fluorene derivative portion in the polymer.

Example 14 Formulas (Ic-1) and (Id-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = 2- ( Synthesis of polymers having a repeating structure of 2-thienyl) pyridine (thpy)

The procedure was as described in Example 10, in which 2.5 mol% of 3,5-linked uncomplexed salicylic-N-hexylimine repeat units irregularly incorporated into the polymer were mixed in a mixture of 1 ml methanol and 30 ml chloroform. 300 mg of ligand polymer (M _w = 89,700) containing, 17 mg (0.015 mmol) of sodium (th-) ₂ Ir (μ-Cl) ₂ Ir (thpy) ₂ and 1.7 mg (0.031 mmol) of sodium methanolate were used. The reaction time was 12 hours under reflux. After completion of the workup, the product was again taken up in CH ₂ Cl ₂ (10 mL) and introduced into a 1: 1 mixture of acetone and methanol (400 mL) to precipitate. Suction filtration and vacuum drying with oil pump gave 232 mg of product (yellow, fibrous).

The polymer contained 2.5 mol% iridium complex in the polymer backbone, based on the fluorene derivative portion in the polymer.

The product gave a white luminescence upon exposure to UV radiation (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Example 15 Formulas (Ic-1) and (Id-1) (Ar ¹ = 2,7- (9,9′-di-n-octyl) fluorenyl, R = hexyl, L ² = phenyl-2 Of polymers having a repeating structure of -pyridine (ppy))

The procedure was the same as described in Example 14, in which 2.5 mol% of 3,5-linked uncomplexed salicylic-N-hexylimine repeat units irregularly incorporated into the polymer were mixed in a mixture of 1 ml methanol and 20 ml chloroform. 300 mg of ligand polymer (M _w = 89,700), 16 mg (0.015 mmol) of (ppy) ₂ Ir (μ-Cl) ₂ Ir (ppy) ₂ and 1.7 mg (0.031 mmol) of sodium methanolate were used. The reaction time was 8 hours under reflux. After completion of the workup, 189 mg of product (yellow, fibrous) were obtained.

The polymer contained 2.5 mol% iridium complex in the polymer backbone, based on the fluorene derivative portion in the polymer.

The product gave a white luminescence under UV irradiation (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Example 16: Formulas (Ic-1) and (Id-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = hexyl, L ² = 4-fluoro Synthesis of polymers having a repeating structure of rophenyl-2-pyridine (fpp))

The procedure was the same as described in Example 14, in which 2.5 mol% of 3,5-linked uncomplexed salicylic-N-hexylimine repeat units irregularly incorporated into the polymer were mixed in a mixture of 1 ml methanol and 20 ml chloroform. a ligand-containing polymer _{(M w = 89,700) 300 mg} , (fpp) 2 Ir (μ-Cl) 2 Ir (fpp) 2 17.1 mg (0.015 mmol) and sodium methanolate 1.7 mg (0.031 mmol) that was used. The reaction time was 8 hours under reflux. After completion of the workup, 175 mg of product (yellow, fibrous) were obtained.

The polymer contained 2.5 mol% iridium complex in the polymer backbone, based on the content of fluorene derivatives in the polymer.

The product gave a white luminescence under UV irradiation (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Example 17: Repeating Units of Formula (Ic-1) and Various Repeating Units of Formula (Id-1) (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R = Synthesis of polymers with hexyl, L ² = phenyl-2-pyridine (ppy) or 2-benzo [b] thiophen-2-yl-pyridine (bthpy)

The procedure was the same as described in Example 14, in which 2.5 mol% of 3,5-linked uncomplexed salicylic-N-hexylimine repeat units irregularly incorporated into the polymer were mixed in a mixture of 1 ml methanol and 20 ml chloroform. Ligand polymer containing 200 mg, (ppy) ₂ Ir (μ-Cl) ₂ Ir (ppy) ₂ 3.3 mg (3.1 μmol), (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ 0.3 mg (0.24 μmol) and 1 mg (0.02 mmol) of sodium methanolate were used. The reaction time was 8 hours under reflux. After completion of the workup, 106 mg of product (yellow) was obtained.

The polymer together contained 2.5 mol% of the iridium complex in the polymer backbone, based on the content of the fluorene derivative in the polymer. The polymer has two different iridium complexes, ie, bis (phenyl-2-pyridine) iridium-salicylimin ((ppy) ₂ Ir (sal), irregularly incorporated into the conjugated polymer backbone, having spectroscopically different emission properties. ) And bis (2-benzo [b] thiophen-2-yl-pyridine) iridium salicylimin ((bthpy) ₂ Ir (sal)). The ratio of (ppy) ₂ Ir (sal) to bthpy ₂ Ir (sal) was about 93: 7.

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

The product gave white luminescence under UV lamp (366 nm).

Example 18 Synthesis of Polymer of Formula (Ia-2) (Ar ¹ = 2,5- (2-ethylhexyloxy) phenylene, R = methyl, L ² = phenyl-2-pyridine (ppy))

The procedure was as described in Example 14, 250 mg of ligand polymer (M _w = 48,300) containing 2 mol% of the terminal benzoylacetone ligand group in a mixture of 1 ml methanol and 15 ml chloroform (ppy) ₂ Ir. 19 mg (0.018 mmol) of (μ-Cl) ₂ Ir (ppy) ₂ and 3 mg (0.55 mmol) of sodium methanolate were used. The reaction time was 22 hours under reflux. After completion of the workup, 206 mg of product (pale yellow, fibrous) were obtained.

The polymer contained 2 mol% end groups. That is, the concentration of the iridium complex was 2 mol% based on the content of the phenylene derivative in the polymer.

The product gave white luminescence under UV lamp (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Film emission spectroscopy: (λ _exc = 370 nm): λ _em = 413, 580 nm

Example 19: Formula (Ia-2) of (Ar ¹ = 2,5- (2-ethylhexyloxy) phenylene, R = methyl, L ² = 4-fluorophenyl-2-pyridine (fpp)) Synthesis of Polymer

The procedure was as described in Example 14, 200 mg of ligand polymer (M _w = 48,300) containing 2 mol% of the terminal benzoylacetone ligand group in a mixture of 1 ml methanol and 15 ml chloroform (fpp) ₂ Ir 18.5 mg (0.016 mmol) of (μ-Cl) ₂ Ir (fpp) ₂ and 2.5 mg (0.04 mmol) of sodium methanolate were used. The reaction time was 12.5 hours under reflux. After workup, 170 mg of product (pale yellow, fibrous) were obtained.

The polymer contained 2 mol% end groups. That is, the concentration of the iridium complex was 2 mol% based on the content of the phenylene derivative in the polymer.

The product gave white luminescence under UV lamp (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Film emission spectroscopy: (λ _exc = 373 nm): λ _em = 413, 597 nm

Example 20:

The polymer according to the invention from Example 11 was tested as the emitter layer in the OLED structure. The following procedure was applied to the production of OLED structures.

1. Structure of ITO substrate:

ITO-coated glass with a surface resistance of 20 ohm / sq (MDT, Merck KgaA) is cut into a 50 mm x 50 mm substrate, and 2 mm wide and about by photoresist technique and subsequent etching. The 10 mm long ITO lands were structured to remain.

2. Cleaning of ITO Substrate:

The substrate was wiped by hand using an acetone immersed cloth and then washed for 15 minutes in a 3% concentration of mucasol aqueous solution in an ultrasonic bath. Subsequently, the substrate was rinsed 10 times with distilled water and then dried in a centrifuge.

3. Application of Byteron® P layer (hole injection layer)

About 10 ml of a 1.6% concentration of polyethylenedioxythiophene / polysulfonic acid solution (HC Starck GmbH, Bitelon® P TP AI 4083) was filtered (Millipore HV, 0.45). Μm). The cleaned substrate was then placed on a spin coater and the filtered solution was dispersed over the ITO-coated side of the substrate. The supernatant was then centrifugally removed by rotating the turntable at 2,500 rpm for 2 minutes with the cover closed. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. Layer thickness was 50 nm (Tencor, Alphastep 500).

4. Application of emitter layer (light emitting layer):

The polymer described in Example 11 was dissolved in chloroform (1 wt%). The solution was filtered (Millipore HV, 0.45 μm) and dispersed over a dry Bitron® P layer. The supernatant was centrifugally removed by rotating the turntable at 3,000 rpm for 30 seconds, with the cover lifted up the chuck after 10 seconds. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness, including the Bitron® P layer and emitter layer, was 150 nm.

5. Application of metal cathode:

Metal electrodes were applied to the organic layer system by deposition. The deposition apparatus (Edwards) used for this purpose was constructed in an inert gas glovebox (brown). The substrate was placed on a deposition mask with slots 1 mm wide and about 10 mm long with the organic layer facing down. A 30 nm thick Ca layer followed by a 200 nm Ag layer was applied successively from two vaporization boats at a pressure of p = 10 ⁻³ Pa. The deposition rate was 10 s / sec for Ca and 20 s / sec for Ag.

6. Characterization of OLED:

Two electrodes of the organic LED were connected to the power source via electrical leads. The positive electrode was connected to the ITO electrode and the negative electrode was connected to the metal electrode. OLED current and electroluminescent intensity were plotted as a function of voltage. Electroluminescence was detected by a photodiode (EG & G C30809E). The voltage pulse duration was 300 milliseconds in each case. The wait time between voltage pulses was 1 second. The spectral distribution of the electroluminescence (EL) was then measured using a glass fiber spectrometer card (Sentronic CDI-PDA). Luminescence was measured with a luminance meter (LS 100 Minolta). All OLED characterizations were done in a glovebox under inert conditions.

result:

Above 4 V, electroluminescence was detectable. The current density at 1.3 V was 1.3 A / cm ² and the brightness was 180 cd / m ² (efficiency at 12 V: η = 0.014 cd / A). The following CIE color coordinates were calculated from the electroluminescence spectroscopy (see FIG. 3): x = 0.28, y = 0.31. Thus, the color position was close to the colorless point and the emission appeared white.

3: Electroluminescent Spectroscopy from Example 20

Example 21:

The polymer according to the invention from Example 13 was tested as the emitter layer in the OLED structure. The procedure corresponded to the procedure of Example 20 except for paragraph 4.

4. Application of emitter layer

The polymer described in Example 13 was dissolved in toluene (1% by weight). The solution was filtered (Millipore HV, 0.45 μm) and dispersed over a dry Bitron® P layer. The turntable was rotated at 600 rpm for 30 seconds with the cover open to remove the supernatant centrifugally (K. Suess RC-13 spin coater). The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness, including the Bytron® P layer and emitter layer, was 150 nm.

result:

Above 4 V, electroluminescence was detectable. At 11.8 V, the current density was 300 mA / cm ² and the luminance was 260 cd / m ² (efficiency at 11.8 V: η = 0.087 cd / A). The following CIE color coordinates were calculated from the electroluminescence spectroscopy: x = 0.29, y = 0.31. Thus, the color position was close to the colorless point and the emission appeared white.

Example 22:

The polymer according to the invention from Example 12 was tested as the emitter layer in the OLED structure (OLED-a). For comparison, OLED structures including pure polyfluorene blended with 2 mol% bis (phenyl-2-pyridine) -iridium- (salicyl-N-hexylimine) were tested (OLED-b). The two emitter systems contained the same amount (2 mol%) of Ir complex.

Polyfluorene bis (phenyl-2-pyridine) -iridium- (salicyl-N-hexylimine)

The procedure corresponded to Example 20 except for paragraph 4.

4a. Application of the polymer according to the invention from example 12 as an emitter layer

The polymer described in Example 12 was dissolved in toluene (1% by weight). The solution was filtered (Millipore HV, 0.45 μm) and dispersed over dried Bitron® P. The supernatant was centrifugally removed by rotating the turntable at 400 rpm for 30 seconds with the cover closed (K. Sheath RC-13 spin coater). The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness, including the Bytron® P layer and emitter layer, was 150 nm.

4b. Apply polymer blend as emitter layer

69.5 g of polyfluorene (179.1 μmol) of fluorenylene repeat unit and 2.4 mg (3.4 μmol) of bis (phenyl-2-pyridine) -iridium- (salicyl-N-hexylimine) were dissolved in 28.69 g of chloroform. The solution was filtered (Millipore HV, 0.45 μm) and dispersed over a dry Bitron® P layer. The turntable was spun at 200 rpm for 30 seconds to remove the supernatant centrifugally (K. Sheath RC-13 spin coater). The cover was lifted after 10 seconds. The coated substrate was then dried at 110 ° C. for 5 minutes on a hot plate. The total layer thickness, including the Bytron® P layer and emitter layer, was 150 nm.

In the layer structure OLED-a and OLED-b prepared according to 4a and 4b above, a metal layer was provided as a cathode by evaporation as described in Example 20.

result:

Electroluminescence was detectable as soon as above 4 V for OLED-a and only above 5 V for OLED-b. At 12 V, current and brightness were 85 mA / cm ² and 170 cd / m ² for OLED-a and 500 mA / cm ² and 110 cd / m ² for OLED-b, respectively (efficiency at 12 V). : η = 0.2 cd / A (OLED-a) and η = 0.022 cd / A (OLED-b)). The following CIE color coordinates were calculated from the electroluminescence spectroscopy: x = 0.38, y = 0.44 (OLED-a) and x = 0.35, y = 0.34 (OLED-b).

This comparative example showed that the covalent bond of the Ir complex results in an OLED that is more efficient than the mixture of polymer and Ir complex. For example, OLED-a showed 10 times higher efficiency than OLED-b.

Example 23: Formula C-1 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = hexyl, L = 2-benzo [b] thiophen-2- Synthesis of Red-Phosphorescent Polymers of Monopyridine (bthpy)

End group-functionalized (salicyaldehyde-n-hexylimine) poly-2,7- (9,9'-di-n-octyl) -fluorene (M _w = 48,700) containing about 2 mol% of ligand units (D = 2.3); 2,280 mg), (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (114 mg) and sodium carbonate (24.7 mg) with 1,2-dichloroethane (160 mL) and ethanol ( 30 ml) was heated to reflux for 40.5 hours under a nitrogen atmosphere. After work up as in Example 2-a, the product was further reprecipitated from chloroform in acetone / methanol (1: 1). 1,780 mg of a fibrous yellow solid was obtained which was a deep red fluorescence under UV lamp.

Complexation was detected by a ¹ H NMR spectrometer.

Electroluminescence: λ _{em, max} = 612 nm.

Example 24 Formulas A and BI-6 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl, R ⁴ = hexyl, L = 2-benzo [b] thiophen-2-yl-pyridine (bthpy) Synthesis of Red-Phosphorescent Polymer

2,7- (9,9'-di-n-octyl) fluorene unit A and 3,5-crosslinked uncomplexed salicylic-N-hexylimine unit BI-6 were converted to 97.5 (A): 2.5 (BI- Random polyfluorene ligand copolymer (M _w = 119,400 (D = 3.43); 1650 mg), (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (110 mg) And sodium methanolate (9 mg) was heated to reflux under a nitrogen atmosphere for 21 hours in a mixture of chloroform (100 mL) and methanol (2.5 mL). Work up as in Example 23 but the product from chloroform was reprecipitated in acetone / methanol (1: 2). 1,430 mg of fibrous yellow solid was obtained which gave a strong red emission under UV lamp.

Complexation was detected by a ¹ H NMR spectrometer.

Example 25 Various Repeating Units of Formula A and Repeating Units of Formula BI-6 (Ar ¹ = 2,7- (9,9'-di-n-octyl) fluorenyl and 2,5-diphenylene [1.3.4] oxadiazole, R ⁴ = hexyl, L = 2-benzo [b] thi Synthesis of Red-Phosphorescent Polymer with Offen-2-yl-pyridine (bthpy)

2,7- (9,9'-di-n-octyl) -fluorene unit A-1, diphenyloxadiazole unit A-2, and 3,5-crosslinked uncomplexed salicylic-N-hexylimine Random polyfluorene ligand terpolymers containing the unit BI-6 in a molar ratio of 75 (A-1): 23 (A-2): 2 (BI-6) (M _w = 67,000 (D = 2.17); 300 mg), (bthpy) ₂ Ir (μ-Cl) ₂ Ir (bthpy) ₂ (16.9 mg) and sodium methanolate (1.4 mg) in a mixture of chloroform (20 mL) and methanol (1 mL) for 15 hours. Heated to reflux under a nitrogen atmosphere. Post-treatment as in Example 23. 163 mg of fibrous yellow solid was obtained which gave a strong red fluorescence under UV lamp.

Complexation was detected by a ¹ H NMR spectrometer.

Film emission spectroscopy: (λ _exc = 399 nm): λ _{em, max} = 619 nm.

Example 26 Synthesis of Yellow-Phosphorescent Polymer of Formula C-1 (Ar ¹ = 2,5- (1-ethylhexyloxy) phenylene, R ⁴ = hexyl, L = phenyl-2-pyridine (ppy))

200 mg, (ppy) ₂ Ir (μ) ligand polymer (M _w = 18,200; D = 1.99) containing about 5 mol% of terminal salicylic-N-hexylimine ligand groups in a mixture of 1 ml methanol and 20 ml chloroform -Cl) ₂ Ir (ppy) ₂ 25.6 mg (0.024 mmol) and sodium methanolate 3 mg (0.55 mmol) were used. The reaction time was 9 hours under reflux. Post-treatment according to example 23 gave 130 mg of the product (yellow powder).

The product gave a strong yellow luminescence under UV lamp (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Film emission spectroscopy: (λ _exc = 446 nm): λ _{em, max} = 580 nm

Example 27: of Formula C-3 (Ar ¹ = 2,5- (1,4-dioctyloxy) phenylene, R ⁵ = methyl, L = 4-fluoro-phenyl-2-pyridine (fpp)) Synthesis of Green-Phosphorescent Polymer

Ligand polymer (M _w = 22,100; D = 1.86) 600 mg, (fpp) ₂ Ir (μ-Cl) ₂ containing about 2 mol% of the terminal benzylacetylacetone ligand group in a mixture of 1 ml methanol and 30 ml chloroform 28 mg (0.024 mmol) Ir (fpp) ₂ and 2.7 mg (0.05 mmol) sodium methanolate were used. The reaction time was 26.5 hours under reflux. After workup according to example 23, 515 mg of product (yellow powder) were obtained.

The product gave a strong green luminescence under UV lamp (366 nm).

Complexation was characterized and detected by ¹ H NMR (400 MHz, CDCl ₃ / TMS, 25 ° C.).

Film emission spectroscopy: (λ _exc = 362 nm): Weak residual fluorescence from conjugated polymer at λ _{em, max} = 502 nm, 422 nm.

Example 28:

The polymers according to the invention from Examples 23 and 24 were tested as emitter layers in OLED structures, respectively. OLED structures were prepared by the procedure according to Example 20. For comparison, 0.95 mol% (Comparative 1) or 1.9 mol% (Comparative 2) bis (2-benzo [b] thiophen-2-yl-pyridine) -iridium- (salicyl-N-hexylimine) ( Two OLED structures were tested, including pure polyfluorene blended with bthpy) ₂ Ir (sal).

Polyfluorene (bthpy) ₂ Ir (sal)

result:

Polymer Example 1% concentration solution Thickness of polymer layer Maximum point of EL emission Color coordinates Voltage Current density EL strength efficiency nm nm x y V mA / cm ² cd / m ² cd / A 23 toluene 100 612 0.639 0.323 10.9 20.0 130 0.65 24 toluene 100 623 0.656 0.321 9.5 8.2 98 1.2 24 toluene 50 617 0.635 0.319 9.0 340 412 0.12 Comparison 1 chloroform 100 615 0.510 0.287 10.0 0.02 << 1 n.d. Comparison 2 chloroform 100 615 0.557 0.320 10.0 0.08 << 1 n.d. (n.d. = not measurable)

The results showed that high EL strength and high efficiency are achieved by the phosphorescent polymer according to the invention in the OLED structure. The results also showed that the EL strength and efficiency can be varied by varying the layer thickness.

The results also showed that covalently bonded Ir complexes resulted in substantially higher luminance at similar voltages than molecular Ir complexes added as dopants to the same polymer matrix. Thus, the polymers 23 and 24 according to the invention were considerably more efficient than the polymers with molecular dopants (Comparatives 1 and 2).

The present invention relates to phosphorescent or luminescent conjugated polymers which are emitted from the phosphorescence of covalently bonded metal complexes, optionally together with the fluorescence of the polymer chain, methods for their preparation and their use in electroluminescent devices.

Electrically conductive organic and polymeric materials are increasingly used in the optoelectronic field, such as, for example, light emitting diodes (LEDs), solar cells, laser diodes, field effect transistors and sensors.

In addition to devices based on low molecular weight organic compounds applied by deposition (Tang et al., Appl. Phys. Lett . 1987, 51, 913), polymers in electroluminescent devices, such as poly (p- Phenylene) (PPP), poly (p-phenylenevinylene) (PPV) and poly-2,7- (fluorene) (PF) have been disclosed (see, eg, A. Kraft et al., Angew. Chem. Int. Ed . 1998, 37, 402].

Light emission in organic light emitting diodes generally occurs preferably through a fluorescence process. However, the electroluminescence (EL) quantum efficiency of devices containing fluorescent emitters is a low theory of singlet excitons (25%) versus triplet excitons (75%), which are formed by electron-hole recombination. Limited by the ratio, because light emission only occurs from a singlet excited state. The advantage of the phosphorescent emitter is that both singlet and triplet states contribute to light emission. That is, since all excitons can be used for light emission, the internal quantum efficiency can be 100% or less.

In general, organic electroluminescent (EL) devices comprise one or more layers comprising an organic charge transport compound in addition to the light emitting layer. The basic structure of these layers in order is as follows.

1.carrier, substrate

2. Bottom electrode

3. Hole injection layer

4. Hole transport layer

5. Light emitting layer

6. electron transport layer

7. Electron injection layer

8. Upper electrode

9. Contact

10. Cover, Encapsulation

The layers 1 to 10 constitute an electroluminescent device. The layers 3 to 7 constitute an electroluminescent device. A hole blocking layer may additionally be present between the light emitting layer 5 and the electron transport layer 6.

This structure represents the most common case and can be simplified by eliminating individual layers so that one layer can perform several tasks. In the simplest case, the EL device is composed of two electrodes, with an organic layer in between performing all functions including light emission.

Multilayer systems of LEDs can be manufactured by chemical vapor deposition (CVD) or casting methods where layers are applied successively from the gas phase. Chemical vapor deposition methods are used in conjunction with shadow mask techniques for the fabrication of structured LEDs using organic molecules as emitters. However, this gas phase process, which must be carried out in a vacuum and cannot be run continuously, is expensive and time consuming. Applications from solutions such as casting (eg, spin coating) and all types of printing methods (inkjet, flexographic printing, screen printing, etc.) can result in faster process speeds, lower device complexity and associated cost savings. Generally preferred. Printing techniques for constructing polymer emitters, in particular inkjet techniques, are currently attracting much attention (Yang et al. Appl. Phys. Lett . 1998, 72 (21), 2660) and WO 99 / 54936).

The incorporation of phosphorescent dopants into organic LEDs has been proposed for increasing the efficiency of electroluminescent devices. When a bis (2-phenylpyridine) iridium (III) acetylacetonate [(ppy) ₂ Ir (acac)] complex emitting green phosphorescence was used as the dopant in the EL device, an external EL efficiency of 19% was measured ( C. Adachi et al., J. Appl. Phys . 2001, 90, 5048).

To date, electroluminescent devices comprising phosphorescent dopants (“small molecules”) have been mainly described. Generally, metal complexes (e.g., iridium (III) complexes or platinum (II) complexes cyclometalized via carbon-nitrogen) that emit phosphorescence at room temperature are irregular in organic molecules or polymer matrices by vacuum evaporation methods. Is dispersed. In addition, doping can be achieved by dissolving the dopant and the organic matrix together in a solvent and then applying it by a casting method (eg, S. Lamansky, Organic Electronic 2001, 2, 53).

Soluble low molecular weight iridium complexes with bulky fluorenyl-pyridine or fluorenyl-phenylpyridine ligands that can be applied from solution but with only a very low 0.1% EL efficiency in EL devices have been recently synthesized (JC Ostrowski et al., Chem. Commun . 2002, 784-785].

A disadvantage of the low molecular weight phosphorescent emitter materials in the EL device is the extinction process, in particular the reduction of the luminous efficiency, especially at relatively high current densities, which is due to the saturation of the emission center due to long phosphorescence duration and / or ) Due to the migration process of the dopant (MA Baldo et al., Pure Appl. Chem . 1999, 71 (11), 2095).

It has recently been reported that the phosphorescent metal complex is directly covalently linked to the polymer. U.S. Patent No. 0015432 A1 describes iridium metal complexes complexed with conjugated polymer backbones via diaza- (bipyridyl) ligands. The polymers described are filled and surrounded by counter ions (polyelectrolytes), which cause movement in the electric field, which adversely affects the stability of the device. However, the light emission of these polymers is limited to the orange or red spectral range. European Patent No. 1 138 746 A1 describes branched conjugated or partially conjugated polymers which may contain phosphorescent metal complexes, but due to the monomers selected, interference in the conjugates and resulting undesired shortening of the conjugate lengths occur. This adversely affects the transport of charge carriers by the layer. In addition, because of the use of iridium-monomer mixtures, it is impossible to produce a polymer with a defined composition, which is also disadvantageous for charge carrier transport by layer. WO 01/96454 A1 describes an aromatic repeating unit based polymer matrix which may contain a light emitting metal complex.

To produce high luminous efficiency polymer LEDs, processed by simple and economical casting or printing methods, efficient electrophosphorescent polymer emission which can result in high external quantum efficiency and long life in OLED (OLED = organic light emitting diode) devices. Sieve material is highly required.

It is therefore an object of the present invention to provide an improved phosphorescent polymer that is suitable for use as an emitter material in LEDs, for example, and that can be applied from solution.

In particular, white organic light emitting diodes, i.e. organic diodes emitting white light, are increasingly attracting attention for the production of full-color displays as an economical backlight for liquid crystal screens, as a source of flat illumination or by color filter combinations.

There are various possibilities and concepts for generating white light using organic light emitting diodes. White light can be produced by additive color mixing of red, green and blue, which are the three primary colors, or by mixing complementary colors, for example blue and yellow light. Light emitting diodes appear white when they emit very wide and uniformly over the entire visible light spectral region of 400 to 800 nm.

Such release is usually not feasible using a single emitter material, so a mixture of emitter materials (components) of different colors must be used. In order to achieve uniform and separate emission of emitters of different colors, it has been found advantageous to select the structure of the light emitting diodes so that the individual emitter materials are separated from one another in different layers. In the absence of such separation, an energy transfer process, which can be barely controlled, for example, between blue and green or red emitters, generally occurs, which reduces the blue component and increases the red component (eg , European Patent EP-A 1 182 244). However, separation of emitters in different layers is also not easy because it is necessary to allow charge carrier recombination as a pretreatment for release to occur in an efficient and balanced manner in all layers. This leads to complex multilayer structures that contain additional intermediate layers (eg, intermediate layers for localization of excited states in each layer) which are expensive and not very attractive for mass production.

White polymer light emitting diodes are disclosed that contain blue-emitting polymers such as polyfluorene or polyvinylcarbazole, and suitable red or orange doping dyes. Dopant concentrations should be established very accurately, often only on the order of hundreds (Kido et al., Applied Physics Letters 1995, 67 (17), 2281). In the case of doping, there is always a risk of long term stability deterioration due to separation, crystallization and / or migration of the low molecular weight dopant in the emitter layer.

The selection of multiple emitter components introduces further serious disadvantages of the so-called "differential aging" of the individual emitter components. That is, the individual emitters decay rapidly to a different degree, causing a shift to a color position away from the white point, sometimes referred to as the achromatic point.

Many white light emitting diodes known to date show the dependence of the color position on the applied voltage and the luminous intensity since in each case various emitter components with different current-voltage-brightness are used.

To date, only two examples based on polymeric white one-component emitter materials have been described in the literature.

Lee et al., Applied Physics Letters 2001, 79 (3), 308 disclose a copolymer comprising oxadiazole, phenylene-vinylene and alkyl ether units, which emit white light in a single layer light emitting diode. Is described. The maximum efficiency is only 0.071 cd / A, the operating voltage is very high, the current flow is low, and the light emitting diode exhibits a significant dependence of the color position on the voltage (12V blue-green, 20V virtually white). Zhan et al., Synthetic Metals 2001, 124, 323 disclose an air comprising dietinylfluorene and thiophene units that emit white light in a two-layer structure (copper phthalocyanine hole injection layer and polymer emitter layer). Coalescence is studied. External quantum efficiency is only 0.01%, electroluminescence can only be detected at voltages above 11V, and current flow through the device is low (23.7 mA / cm ² at 19V). Due to their low efficiency and unsatisfactory current-voltage-brightness characteristics, the two examples are not suitable for industrial use.

It is a further object of the present invention to provide a one-component emitter material which emits white light and can be processed from solution. The emitter material should preferably exhibit efficient white emission in the simple device structure itself, for example in a two-layer structure (hole injection layer and emitter layer).

Surprisingly, the inventors have found that conjugated and neutral phosphorescent polymers containing one or more covalently bound phosphorescent metal complexes are suitable as emitter materials, for example for use in the above-mentioned LEDs, and can be applied from solution. .

Accordingly, the present invention relates to phosphorescent polymers which contain at least one covalently bound phosphorescent metal complex and are conjugated and neutral.

Conjugated herein means that the backbone of the polymer may be fully conjugated or partially conjugated. Wide conjugated lengths in the backbone are advantageous due to good charge carrier transport, and therefore polymers having such conjugated lengths, in particular polymers with fully conjugated backbones, are preferred.

As used herein, "the phosphorescent conjugated polymers according to the invention are preferably straight chain" in some cases they serve as covalent linkages of phosphorescent metal complexes but will contain only short side chains which are not branching points as they are not growth sites of the polymer. That means you can.

The phosphorescent conjugated polymer according to the invention exhibits phosphorescence as a result of electrophosphorescence, ie electrical excitation, for example in OLEDs. However, they can also cause phosphorescence by optical excitation.

These are phosphorescent conjugated polymers containing at least one phosphorescent metal complex covalently bound via at least one ligand L ¹ which is a unit selected from formulas (I)-(XXIXc).

In the above formula,

R is the same or different and independently from each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and substituted with nitrogen, oxygen and sulfur, substituted with a C ₅ -C ₂₀ -aryl unit and / or optionally substituted with C ₁ -C ₃₀ -alkyl substituted with an alkyl A heteroaryl unit having 1 to 3 atoms in the ring, and / or a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group , A nitro group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group, or an alkyl- or arylcarbonyl group, wherein alkyl is C ₁ -C ₃₀ -alkyl and aryl is C ₅ -C ₂₀ -aryl),

Ar is an optionally substituted phenylene, biphenylene, naphthylene, thienylene and / or fluorenylene unit.

In the phosphorescent conjugated polymer according to the present invention, L ¹ may be a component of a conjugated main chain covalently bonded directly to the main chain as one of the above-described side chains or covalently bound to the main chain via a linker referred to below as a spacer Or may be a component of the end groups of the polymer.

In the phosphorescent conjugated polymer according to the invention, L ¹ is preferably one component of the conjugated backbone or one component of the terminal group.

In a preferred embodiment of the invention, L ¹ in the phosphorescent conjugated polymer according to the invention is one component of the end group.

When coordinated with the metal center, H is can be removed optionally from the ligand unit L ¹ in the coordination sites, L ¹ of the phosphorescent conjugated polymers according to the present invention exhibits the aforementioned structure without H atoms thereof optionally removed. This may be the case in particular from the original hydroxyl groups coordinated via the carbon coordination site and the oxygen coordination site. The same applies to the ligands L ² and L mentioned immediately below.

The present invention particularly preferably relates to phosphorescent conjugated polymers containing repeating units of the formulas (A) and (B-I) or (A) and (B-II) or having structures of the formula (C) or (D).

In the above formula,

Ar ¹ , Ar ² and Ar ³ are the same or different and independently of one another are C ₅ -C ₂₀ -aryl units optionally substituted with C ₁ -C ₃₀ -alkyl and / or optionally C ₁ -C _30- A heteroaryl unit having 5 to 9 carbon atoms in the ring substituted by alkyl and having 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur,

L ¹ and L ² are the same or different,

L ¹ has ^one of the above meanings, where for structures B-II, C and D one of the two linking positions is H, F, CF ₃ , linear or branched C ₁ -C ₂₂ A C ₅ -C ₂₀ -aryl unit optionally substituted with a -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, C ₁ -C ₃₀ -alkyl and / or optionally C ₁ -C ₃₀ -alkyl Substituted, saturated or linear or branched partial fluorination by heteroaryl units having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms from the ring consisting of nitrogen, oxygen and sulfur, or Perfluorinated C ₁ -C ₂₂ -alkyl groups, linear or branched C ₁ -C ₂₂ -alkoxycarbonyl groups, cyano groups, nitro groups, amino groups, alkylamino groups, dialkylamino groups, arylamino groups, diarylamino groups or alkylarylamino groups Saturated or alkyl- or arylcarbonyl groups Standing, alkyl is C ₁ -C ₃₀ - alkyl and aryl is C ₅ -C ₂₀ - is saturated by aryl),

L ² is L ¹ and are independently as one of the above-mentioned means for the L ^1, connected to the position of the case does not exist independent of each other two connecting position or the second connecting position is H, F, CF _3, linear or It branched C ₁ -C ₂₂ - alkyl group, a linear or branched C ₁ -C ₂₂ - alkoxy groups, optionally C ₁ -C ₃₀ - a C ₅ -C ₂₀ substituted alkyl-aryl units, and (or) optionally at least one C Saturated by a heteroaryl unit having 5 to 9 carbon atoms in the ring, substituted with _1- C ₃₀ -alkyl, and having 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen, and sulfur; Or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group, nitro group, amino group, alkylamino group, dialkylamino group, arylamino group, dia Saturated by an arylamino group or an alkylarylamino group , Or an alkyl- or arylcarbonyl group (wherein alkyl is C ₁ -C ₃₀ - alkyl and aryl is C ₅ -C ₂₀ - aryl) is saturated by,

The linking position should be understood to mean the position indicated by * in Formulas I to XXIX,

Ligands L ¹ and L ² complex the metal M in a chelate-like manner,

M is iridium (III), platinum (II), osmium (II), gallium (III) or rhodium (III),

n is an integer from 3 to 10000,

z is an integer from 0 to 3,

Sp is a spacer, in particular a linear or branched C ₂ -C ₁₅ - alkylene or C ₂ -C ₁₅ units in one to three heteroatoms in the chain, from the group consisting of nitrogen, oxygen and sulfur-heteroaryl-alkylene units, C ₅ -C ₂₀ -arylene units and / or heteroarylene units having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, or C _1- C ₁₂ -alkylenecarboxylic acid unit or C ₁ -C ₁₂ -alkylenedicarboxylic acid unit or C ₁ -C ₁₂ -alkylenecarboxamide unit or C ₁ -C ₁₂ -alkylenedicarboxamide unit to be.

Formula D is understood herein to form copolymer chains containing repeat units -Ar ¹ -and -Ar ² -that are different from Ar ¹ and Ar ^{2 and} are alternately or in block or irregularly distributed. The copolymer chain may contain 0.1 to 99.9% of repeating units -Ar ¹ -and 0.1 to 99.9% of repeating units -Ar ² -with a total of 100%. The total number of all repeat units -Ar ¹ -and -Ar ² -in the polymer is n.

When Ar ² and Ar ³ in the repeating unit B-Ia are identical to Ar ¹ in the repeating unit A, the phosphorescent conjugated polymer according to the present invention, corresponding to the above formulation, contains repeating units of the formulas A and B-Ib .

In the above formula,

Ar ¹ , L ¹ , L ² , M and z have the above meanings.

For the purposes of the present invention, the polymers according to the invention containing repeating units of formulas A and BI, ie B-Ia and B-Ib or B-II, are also in each case a number of different units of formula A, in particular 2 It may contain different units of species, ie many different units of formula A and units of formula B, ie B-Ia and B-Ib or B-II.

The invention also particularly preferably

Ar ¹ , Ar ² and Ar ³ are the same or different and independently from each other thiophene units of the formulas XXX and XXXI, benzene, biphenyl and fluorene units of the formulas XXXII to XXXIV and / or the following formulas XXXV to A heterocycle of XXXXXIV and / or a unit selected from units of the formulas XXXXXV to XXXXXXIII, wherein L ¹ and L ² are the same or different and have the above meanings and M, n, z and Sp have the above meanings And phosphorescent conjugated polymers containing repeating units of formulas A and B-Ia, A and B-Ib, or A and B-II or having the structure of formula C or D.

In the above formula,

R is the same or different and independently from each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and substituted with nitrogen, oxygen and sulfur, substituted with a C ₅ -C ₂₀ -aryl unit and / or optionally substituted with C ₁ -C ₃₀ -alkyl substituted with an alkyl A heteroaryl unit having 1 to 3 atoms in the ring, and / or a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group , A nitro group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group, or an alkyl- or arylcarbonyl group, wherein alkyl is C ₁ -C ₃₀ -alkyl and aryl is C ₅ -C ₂₀ -aryl).

They are particularly preferably Ar ¹ , Ar ² and Ar ^{3 which} are the same or different and independently from each other thiophene units of the formulas XXX and XXXI, benzene, biphenyl and fluorene units of the formulas XXXII to XXXIV and / or Is a unit selected from units of formulas XXXXXVI to XXXXXX, and L ¹ and L ² are units selected from formulas I, II, III, VIII, XVIII, XX, XXI, XXIII, XXIV, XXVIIa, XXVIII, XXIX and XXIXa , M is osmium (II), iridium (III), platinum (II) or rhodium (III), n is an integer from 5 to 500, z is an integer from 1 to 3, Sp is C ₁ -C _6- alkylene or C ₁ -C ₆ - alkylene carboxylic acids or C ₁ -C ₆ - alkylene dicarboxylic acids, the repetition of the formula a and B-Ia, Ib-a and B, or a and B-II Phosphorescent conjugated polymers containing units or having the structure of formula (C) or (D).

In said formula, R is one of the said meanings.

They very particularly preferably contain repeating units selected from the following formulas A and BI-1 to BI-6 or A and B-II-1 to B-II-4 or the following formulas C-1, C-2 or C -3 or a phosphorescent conjugated polymer having a structure of D-1, D-2 or D-3.

In the above formula,

Ar ¹ is Unit selected from, preferably Unit selected from

Ar ² is Unit selected from

L is

Is a ligand selected from

R ¹ is dodecyl,

R ² is n-octyl and 2-ethylhexyl,

R ³ is methyl and ethyl,

R ⁴ is methyl and n-hexyl,

R ⁵ is methyl and phenyl,

R ⁶ is H, a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched C ₁ -C ₂₂ -alkoxy group,

Z is a CH ₂ or C═O group,

n has the above meaning.

In a preferred embodiment of the invention, L or L ² is particularly

Ligand selected from.

The resulting phosphorescent polymers according to the invention are particularly suitable as red emitters.

A repeating unit B which represents the formula BI (ie B-Ia or B-Ib) or B-II and represents the preferred formulas BI-1 to BI-5 or BI-6 or B-II-1 or B-II-4; The sum total of the number of repeating units A is p, p is an integer of 3-10000, Preferably 5-500. Repeating units A and B may be distributed alternately or in block form or irregularly in the polymer. The content (percentage) of the repeating unit A based on the total number of repeating units in the polymer may be 0 to 99.9%, preferably 75.0 to 99.9%, and the content (percentage) of the repeating unit B based on the total number of repeating units in the polymer ) May be 0.1 to 100%, preferably 0.1 to 25%, provided that the two contents (percentages) add up to 100%.

Herein, all radicals R in the units L ¹ , L ² , Ar ¹ , Ar ² or Ar ^{3 described above} may be the same or different at different units from these units, and also within one of these units It may be the same or different.

The positions denoted by * in all of the above and below formulas are also referred to as linking positions, and should be understood to mean positions at which the linking of each unit to the same or different additional units can be carried out therethrough.

In the end groups of the phosphorescent conjugated polymers according to the invention, preferably according to the invention having, for example, the structure of formula C, C-1 or C-3 or D, D-1, D-2 or D-3 In the case of phosphorescent polymers according to the invention in which the phosphorescent metal complex is bonded via ligand L ¹ , as in the case of phosphorescent polymers, or for example containing repeating units of formulas A and B, the free linking position is preferably H or Aryl, particularly preferably saturated with phenyl.

In one preferred embodiment, the phosphorescent conjugated polymers according to the invention have advantages over known phosphorescent polymers in that they have a defined composition, wherein the defined composition is independent of chain length; The unconjugated ligand polymers as well as the phosphorescent conjugated polymers according to the invention have a constant chain length distribution or molar weight distribution (M _w ). The above defined composition is the result of certain preparations of uncomplexed ligand polymers that can be readily purified, clearly characterized and complexed with the corresponding transition metal precursor complex.

Surprisingly, the inventors have also found that phosphorescent conjugated polymers that fluoresce in the conjugated backbone in addition to the phosphorescence of the covalently bonded phosphorescent metal complex or complexes can emit white light and can be processed from solution.

Such phosphorescent polymers according to the invention are hereinafter referred to as luminescent polymers.

For a better overview, the number of the structure of the light emitting polymer according to the invention and the structure of its components is independent of the structure number of the phosphorescent polymer according to the invention. Since the numbers for the structure of the light emitting polymer according to the invention and the structure of the components thereof are given in parentheses, the number of structures for the phosphorescent polymer according to the invention and for the structure of the components thereof will be readily distinguished.

Accordingly, the present invention relates to a light emitting polymer having a conjugated backbone, containing one or more covalently bonded metal complexes, and emitting light from a combination of fluorescence of the conjugated backbone and phosphorescence of the covalently bonded metal complexes or complexes.

Conjugated herein means that the backbone of the polymer may be fully conjugated or partially conjugated. Large conjugated lengths in the backbone are advantageous due to good carrier transport, with polymers having such conjugated lengths being preferred, in particular polymers with fully conjugated backbones.

The luminescent polymers according to the invention are preferably straight chains, which here in some cases serve as covalent linkages of phosphorescent metal complexes but may contain only short side chains which are not branching points as they are not growth sites of the polymer. it means.

The light emitting polymers according to the invention exhibit light emission, for example in OLEDs, as a result of electroluminescence, ie electrical excitation. However, they can also cause luminescence by optical excitation.

The light emitting polymer according to the invention preferably emits white light. Herein, the white light has a variable chromaticity diagram according to CIE 1931 (Commission Internationale de l'Eclairage), wherein the value of color coordinate x may be 0.20 to 0.46 and the value of color coordinate y may be 0.20 to 0.46 irrespective of x. It should be understood as meaning light defined by the color position in the chromaticity diagram. This is defined herein as the color coordinates x = 0.33 ± 0.13 and y = 0.33 ± 0.13 in the variable chromaticity table according to CIE 1931, where the white light can be the same or different values of x and y independently of each other from 0.20 to 0.46. White or white pseudo light with a color position. The numerical range mentioned for the color coordinates is a continuous numerical range. Particularly preferably, the luminescent polymer according to the invention has a color position in the variable chromaticity table according to CIE 1931, in which the value of the color coordinate x can be 0.28 to 0.38 and the value of the color coordinate y can be 0.28 to 0.38 irrespective of x. Emits white light as defined by

Herein, the emission light is a combination of the fluorescence of the conjugated backbone and the phosphorescence of the covalently bonded metal complexes or complexes, and in each case their emission light may differ from white in color, which is also preferred. Additive color mixing of only the primary colors of red, green, and blue emission light or additive color mixing of the complementary complementary colors makes the emission light appear entirely white.

Preferably, the present invention relates to a light emitting polymer wherein metal complexes or complexes, which may be the same or different, are covalently bonded to the chain ends of the conjugated backbone.

These are particularly preferably light emitting polymers having the structure of formula (Ia) or (Ib).

In the above formula,

Ar ¹ is optionally substituted with the following phenylene units (IIa) or (IIb), biphenylene units (IIc), fluorenylene units (IId), dihydroindenofluorenylene units (IIe), spirobifluores A unit selected from a nylene unit (IIf), a dihydrophenanthrylene unit (IIg) or a tetrahydropyrenylene unit (IIh),

Ar ² is different from Ar ¹ and is a unit selected from the following formulas (IIa) to (IIq),

L ¹ and L ² are the same or different at each occurrence,

L ¹ is a ligand of formulas (IIIa-1) to (IIId-1),

Ar is a unit selected from optionally substituted phenylene, biphenylene, naphthylene, thienylene or fluorenylene units,

L ² is L ¹ and is to independently a ligand selected from units of the formula (IVa-1) to (IVy-1), ligand L ¹ and L ² are sikimyeo complexing the metal M with a chelating similar manner,

M is iridium (III), platinum (II), osmium (II) or rhodium (III),

n is an integer from 3 to 10000, preferably from 10 to 5000, particularly preferably from 20 to 1000, very particularly preferably from 40 to 500,

z is an integer from 1 to 3,

R is the same or different radicals and, independently of one another, H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group , linear or branched C ₁ -C ₂₂ - alkoxy groups, optionally C ₁ -C ₃₀ di-substituted by an alkyl-substituted with an alkyl C ₅ -C ₂₀ - aryl units, and (or) optionally at least one C ₁ -C ₃₀ Or a heteroaryl unit having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, and / or linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group, nitro group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group or alkylarylamino group, or alkyl- or Arylcarbonyl group (here Alkyl is C ₁ -C ₃₀ - alkyl and aryl is C ₅ -C ₂₀ - is aryl).

In the formulas (Ia) and (Ib) and below, the light emitting polymer preferably has a constant molar weight distribution, so it is to be understood that n means the average value of the repeating units.

When coordinated with the metal center, H is a ligand unit of L ¹ or L can be optionally removed from the ^2, L ¹ of the phosphorescent conjugated polymers according to the present invention structure in the no H atoms thereof optionally removed from the coordination sites Indicates. This may be the case in particular from the original hydroxyl groups coordinated via the carbon coordination site and the oxygen coordination site.

These are very particularly preferably light emitting polymers having the structure of formulas (Ia-1), (Ia-2), (Ib-1), (Ib-2), (Ia-3) or (Ib-3).

In the above formula,

R is a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched partially fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group,

n, Ar ¹ , Ar ² and L ² have the above meanings.

As used herein, the formula (Ib-1), (Ib -2) and (Ib-3) is repeated in the Ar ¹ and Ar ² are different and, alternately or in the form of block or randomly distributed units -Ar ¹ - And to form a copolymer chain containing -Ar ^2- , wherein the copolymer chain is 0.1 to 99.9% of the repeating units -Ar ¹ -and 0.1 to 99.9% of the repeating unit, the sum of which is 100%. Ar ² -may be contained. The total number of all repeat units -Ar ¹ -and -Ar ² -in the polymer is n.

The invention also relates to a light emitting polymer wherein the metal complex or complexes, which may preferably be the same or different, are covalently bonded to the conjugate backbone.

These are particularly preferably light emitting polymers containing n repeating units of the formulas (Ic-1) and (Id) or (Ic-1), (Ic-2) and (Id).

In the above formula,

Ar ¹ is optionally substituted with the following phenylene units (IIa) or (IIb), biphenylene units (IIc), fluorenylene units (IId), dihydroindenofluorenylene units (IIe), spirobifluores A unit selected from a nylene unit (IIf), a dihydrophenanthrylene unit (IIg) or a tetrahydropyrenylene unit (IIh),

Ar ² is different from Ar ¹ and is a unit selected from the following formulas (IIa) to (IIq),

L ¹ and L ² are the same or different at each occurrence,

L ¹ is a ligand of formulas (IIIa-2) to (IIIi-1)

L ² is L ¹ and is in the following as a ligand selected from units of the formula (IVa-1) to (IVy-1) independent of the ligand L ¹ and L ² and is complexed with the metal M chelate similar manner,

M is iridium (III), platinum (II), osmium (II) or rhodium (III),

n is an integer from 3 to 10000, preferably from 10 to 5000, particularly preferably from 20 to 1000, very particularly preferably from 40 to 500,

z is an integer from 1 to 3,

R is the same or different radicals and, independently of one another, H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group , linear or branched C ₁ -C ₂₂ - alkoxy groups, optionally C ₁ -C ₃₀ di-substituted by an alkyl-substituted with an alkyl C ₅ -C ₂₀ - aryl units, and (or) optionally at least one C ₁ -C ₃₀ Or a heteroaryl unit having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, and / or linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group, nitro group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group or alkylarylamino group, or alkyl- or Arylcarbonyl group (here Alkyl is C ₁ -C ₃₀ - alkyl and aryl is C ₅ -C ₂₀ - is aryl).

These are very particularly preferably light emitting polymers containing n repeating units of the formulas (Ic-1) and (Id-1).

In the above formula,

R is a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched partially fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group,

n, Ar ¹ and L ² have the above meanings.

When (Ic) represents formulas (Ic-1) or (Ic-1) and (Ic-2) and (Id) represents formulas (Id) or (Id-1), repeating units (Ic) and (Id) ) Is the sum of n, n is an integer from 3 to 10000, preferably from 10 to 5000, particularly preferably from 20 to 1000, very particularly preferably from 40 to 500, wherein n is defined herein It is always to be understood that the light emitting polymer according to the invention means an average value of repeating units, since it may preferably have a constant molar weight distribution.

The repeating units (Ic) and (Id) may be distributed alternately or in block form or irregularly in the polymer. Based on the total number of repeating units in the polymer, the content (percent) of repeating units (Ic) may be 0.1 to 99.9%, preferably 75.0 to 99.9%, and based on the total number of repeating units in the polymer, The content (percentage) of the unit (Id) may be 0.1 to 100%, preferably 0.1 to 25%, provided that the two contents (percentages) are 100% combined. In a preferred embodiment, based on the total number of repeat units in the polymer, the content (percentage) of repeat units (Id) can be 0.01 to 15%, preferably 0.01 to 10%, particularly preferably 0.01 to 5%. Therefore, based on the total number of repeating units in the light emitting polymer according to the invention of these preferred embodiments, the content (percent) of repeating units (Ic) is 85 to 99.99%, preferably 90 to 99.99%, particularly preferred Preferably from 95 to 99.99%, which is likewise subject to 100% when the two contents (percentages) are combined. The above percentage data is based on the amount of material (mol%).

In a preferred embodiment of the light emitting polymer according to the invention, L ² is a ligand selected from units of the formula

The light emitting polymers of these preferred embodiments may also optionally contain a ligand selected from units of the formula: in addition to the units described above for L ² .

A further preferred embodiment of the invention is characterized in that Ar ¹ and Ar ² are independently of each other A light emitting polymer according to the present invention wherein R is a linear or branched C ₁ -C ₂₂ -alkyl group.

Herein, all radicals R in the units L ¹ , L ² , Ar ¹ , Ar ² or Ar ^{3 described above} may be the same or different at different units from these units, and also within one of these units It may be the same or different.

The positions indicated by * in all of the above and the following formulas are also referred to as linking positions, and should be understood to mean positions at which linkage of each unit to the same or different additional units can be carried out therethrough.

In the terminal group (terminal linking position) of the light emitting polymer according to the present invention, preferably, for example, the formula (Ia) or (Ib) or (Ia-1), (Ia-2), (Ia-3), ( As in the case of the light-emitting polymers according to the invention with structures Ib-1), (Ib-2) or (Ib-3), the phosphorescent metal complexes are bound via ligand L ¹ , or for example formula (Ic) In the case of luminescent polymers according to the invention containing repeating units of) and (Id), the free linking position is preferably saturated with H or aryl, particularly preferably phenyl.

The luminescent polymer according to the invention is obtained when the conjugated polymer backbone and the covalently bonded phosphorescent metal complex or complexes are selected such that the excitation energy is not completely transferred to or remains in the phosphorescent metal complex or complexes. That is, when some excitation energy remains on the conjugated polymer backbone, fluorescence of the conjugated backbone occurs in addition to the phosphorescence of the metal complex or complexes.

This can be explained by way of example of the polymers according to the invention in which the conjugated backbone contains fluorenyl repeat units. For example, when such conjugated polyfluorene backbone is combined with an iridium complex with yellow or green phosphorescence, energy transfer from the polyfluorene backbone to the iridium complex or complexes only occurs incompletely. Part of the excitation energy is converted to the blue fluorescence of the polyfluorene backbone and the other part to the phosphorescence of the iridium complex or complexes.

On the other hand, when the polyfluorene backbone is combined with an iridium complex with red phosphorescence, the red phosphorescence of the iridium complex or complexes occurs exclusively because the excitation energy is efficiently transferred from the polyfluorene backbone to the iridium complex or complexes.

Phosphorescent or luminescent polymers according to the invention can be fractionated based on their emission spectroscopy (eg electroluminescence spectroscopy). The emission spectra of the phosphorescent polymers according to the invention are typically phosphorescent spectroscopy and have a phosphorescent band but no fluorescent band. On the other hand, the emission spectra of the light emitting polymers according to the invention also have fluorescent bands in addition to the phosphorescent bands. FIG. 1 shows a typical electroluminescence spectroscopy of a phosphorescent polymer according to the invention, and FIG. 3 shows a typical electroluminescence spectroscopy of a phosphorescent polymer according to the invention, wherein blue polyfluorene fluorescence and yellow-green iridium phosphorescence are shown. The overlap is clearly evident. On the other hand, Figure 2 is for comparison, electroluminescence spectroscopy showing only the fluorescence band of polyfluorene is shown.

The phosphorescent or light emitting polymer according to the invention exhibits electroluminescence, ie light emission via electrical excitation, for example in OLEDs. However, they can also exhibit optical excitation, ie light emission by light. However, the electroluminescence spectra of the phosphorescent or luminescent polymers according to the invention may differ from their photoluminescence spectroscopy, so that the color of the emitted light may also differ depending on excitation (electrical or optical).

The present invention also relates to an uncomplexed ligand polymer comprising an iridium (III), platinum (II), osmium (II) or rhodium (III) precursor complex, preferably an iridium (III) precursor complex, in particular iridium (III) of formula It relates to a process for the preparation of the phosphorescent or spectroscopic polymers according to the invention which are complexed with precursor complexes.

In the above formula,

L ² has the above meaning.

The activity of the iridium precursor complex of formula E may be necessary in advance, which is a silver (I) salt, in particular silver (I) trifluoromethanesulfo, in an organic solvent or solvent mixture, for example dichloromethane and / or acetonitrile. It is achieved by stirring with the nate. This activity is required, for example, when the ligand L ² complexes the transition metal in a chelate-like manner via both the carbon and nitrogen coordination sites.

Uncomplexed ligand polymers are all polymers containing repeat units of formula A or (Ic) and / or F.

In the above formula,

X may be the above meaning of Ar ¹ , Ar ² , Ar ³ or the above meaning of L ¹ (as defined in formula B-Ia, B-Ib or (Id)) or a combination thereof, and repeating unit A Or the sum of the numbers of (Ic) and / or F is n or p, where n and p have the above meanings. The uncomplexed ligand polymer can be functionalized at the chain end in each case with the ligand L ^{1 or} according to the definition for formula C or D or (Ia) or (Ib), or saturated with H or aryl.

The method also has the advantage of changing the transition metal content, in particular the iridium content, in the polymer in a simple manner through the selection of the chemical equivalent ratio of the ligand polymer to the transition metal precursor complex, in particular the iridium precursor complex.

Synthesis of iridium precursor complexes is described in, for example, S. Sprouse, KA King, PJ Spellane, RJ Watts, J. Am. Chem. Soc. , 1984, 106, 6647-6653 or WO 01/41512 A1. Synthesis of ligand polymers is described by, for example, T. Yamamoto et al., J. Am. Chem. Soc . 1996, 118, 10389-10399, T. Yamamoto et al., Macromolecules 1992, 25, 1214-1223, and RD Miller, Macromolecules 1998, 31, 1099-1103.

The phosphorescent conjugated polymers according to the present invention have advantages over low molecular weight phosphorescent metal complexes in that they can be applied from solution and can be applied in one step without further doping or blending, and at the same time have a long lifetime and high external quantum efficiency in EL devices.

The luminescent polymers according to the invention can likewise be applied from solution and have the advantage that they can be applied in one step without further doping or blending as compared to mixtures of polymers and low molecular weight dopants or mixtures of emitter materials of different colors.

The phosphorescent or light emitting polymer according to the invention also has the advantage that the polymer and the phosphorescent metal complex cannot be separated and the metal complex cannot be crystallized. This separation and crystallization process has recently been described for blend systems consisting of polymers and mixed low molecular weight iridium complexes (Noh et al., Journal of Chemical Physics 2003, 118 (6), 2853-2864).

Surprisingly, the inventors have found that the luminescent polymer according to the invention is suitable as a white one-component emitter material. The white emitters according to the invention are characterized in that they have fluorescent and phosphorescent components in different spectral ranges. They have the advantage of emitting even at low operating and switch-on voltages, exhibit good current-voltage-luminance properties, and are white with high efficiency even in a two-layer diode structure (hole injection layer and emitter layer). Generate light.

Thus, the phosphorescent or light emitting polymers according to the invention are emitter materials in indicators or displays (TVs, computer monitors), light-emitting components such as organic or polymer LEDs, laser diodes, for the back lighting of LCDs and watches. As an illumination element in a flat light source, as a display for household appliances (e.g., washing machines, refrigerators, vacuum cleaners, etc.), as a billboard and information sign in mobile communication devices, for the interior of an instrument panel in the automotive field. It is particularly suitable for use as an integrated display for illumination and illumination, or in displacement systems and the like.

The light emitting polymer according to the invention is a white emitter material in a light emitting component such as a white organic light emitting diode, for example as an economical back light of a liquid crystal display, as a source of planar illumination or by using a color filter in combination with a color filter. It is especially suitable for use for the production of.

Accordingly, the use as phosphor emitter in the light emitting component of the phosphorescent or light emitting polymer according to the invention is also in accordance with the invention.

Compared to low molecular weight emitter materials, in this respect they have the advantage of avoiding quenching processes which lead to a decrease in external quantum efficiency. These mostly occur with increased iridium concentrations (local accumulation) in the case of low molecular weight emitters due to migration processes. In the phosphorescent or light emitting polymers according to the invention, the iridium complexes no longer undergo a migration process due to the covalent linkage to the polymer.

Since the white emitters according to the invention are mono-component emitters, they do not exhibit the disadvantages of the energy transfer process and the aforementioned "differential aging" (degradation of each emitter to different degrees at different rates), resulting in colorless points. It is also advantageous that the shift of the color position away from the white point mentioned is not expected at a relatively long uptime. In addition, the white emitter according to the present invention exhibits no visual indication of the dependence of the color position of the emitted light on the applied voltage.

In order to set or optimize a particular color position, different polymers according to the invention can be blended, for example phosphorescent polymers according to the invention further phosphorescent polymers according to the invention and / or luminescent polymers according to the invention. Can be blended with For example, when white light is produced in complementary blues and yellows, the light appears white but no red spectral component is present, so that the color reproduction of the object illuminated by this light can be modulated. Mixing the red emitting polymer according to the invention may be advantageous in this case. In addition, the red spectral component is absolutely necessary because the red filter filters and removes all the spectral components except red when the red light is generated with the aid of the color filter.

The present invention therefore also relates to blends comprising at least one phosphorescent polymer (s) according to the invention and at least one light emitting polymer (s) according to the invention and to the use as an emitter in the light emitting component of the blend. .

Instead of using blends of phosphorescent and luminescent polymers according to the invention, they can also be applied successively in several layers to achieve corresponding color positioning or color position optimization.

 The invention also relates to an electroluminescent device containing at least one phosphorescent or light emitting polymer according to the invention. The phosphorescent or light emitting polymer according to the invention acts as a light emitting material.

When the phosphorescent or light emitting polymers according to the invention are used as light emitting materials, additional components such as, for example, binders, matrix materials or charge transport compounds are absolutely not necessary in the light emitting layer, but nevertheless these additional components are present. There is an advantage over known low molecular weight light emitting materials in that they can be.

The invention also relates to an electroluminescent device in which at least one according to the invention contains a blend of a phosphorescent polymer and at least one emitting polymer according to the invention.

The present invention preferably relates to an electroluminescent device further comprising a hole injection layer.

These are particularly preferably electroluminescent devices in which the hole injection layer consists of neutral or cationic polythiophenes of the formula (G).

In the above formula,

A ¹ and A ² are independently of each other hydrogen, optionally substituted C ₁ -C ₂₀ -alkyl, CH ₂ OH or C ₆ -C ₁₄ -aryl, or optionally substituted C ₁ -C ₁₃ -alkylene or C ₆ -C ₁₄ -arylene, preferably C ₂ -C ₄ -alkylene, particularly preferably ethylene together,

m is an integer of 2 to 10000, preferably 5 to 5000.

The polythiophenes of the above formula (G) are described in EP-A 0 440 957 and 0 339 340. A description of the preparation of the dispersions or solutions used can be found in European Patent EP-A 0 440 957 and German Patent DE-A 42 11 459.

Polythiophenes are used, for example, in dispersions or solutions in cationic form, obtained by treating neutral thiophenes with oxidizing agents. Conventional oxidants such as potassium peroxodisulfate are used for oxidation. As a result of oxidation, polythiophene acquires a positive charge, which is not shown in the formula because its number and its position cannot be satisfactorily determined. According to the information given in EP-A-0 339 340, they can be produced directly on the carrier.

Preferred cationic or neutral polythiophenes consist of structural units of the formula G-a.

In the above formula,

Q ¹ and Q ² independently of one another are hydrogen, optionally substituted (C ₁ -C ₁₈ ) -alkyl, preferably (C ₁ -C ₁₀ ) -alkyl, in particular (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₁₂ ) -alkenyl, preferably (C ₂ -C ₈ ) -alkenyl, (C ₃ -C ₇ ) -cycloalkyl, preferably cyclopentyl or cyclohexyl, (C ₇ -C ₁₅ ) -Aralkyl, preferably phenyl- (C ₁ -C ₄ ) -alkyl, (C ₆ -C ₁₀ ) -aryl, preferably phenyl or naphthyl, (C ₁ -C ₁₈ ) -alkoxy, preferably (C ₁ -C ₁₀ ) -alkoxy, for example methoxy, ethoxy, n-propoxy or isopropoxy, or (C ₂ -C ₁₈ ) -alkoxy esters, these radicals being substituted with one or more sulfonate groups Can be,

m has the above meaning.

Very particular preference is given to cationic or neutral poly-3,4- (ethylene-1,2-dioxy) thiophenes.

In order to offset the positive charge, the polythiophene in cationic form contains anions, preferably polyanions.

Polyanions which are preferably used are anions of polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid or polymaleic acid, and polymeric sulfonic acids such as polystyrenesulfonic acid and polyvinylsulfonic acid. These polycarboxylic acids and polysulfonic acids may also be copolymers of vinylcarboxylic acids and vinylsulfonic acids with other polymerizable monomers such as acrylic esters and styrene.

Anions of polystyrenesulfonic acid are particularly preferred as counter ions.

The molecular weight of the polyacid providing the polyanion is preferably 1000 to 2000000, particularly preferably 2000 to 500000. Polyacids or alkali metal salts thereof, such as polystyrenesulfonic acid and polyacrylic acid are commercially available or known methods (see, for example, Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry), Vol. E 20, Makromolekulare Stoffe (Macromolecular Substances), Part 2 (1987), page 1141 and below).

Instead of the free polyacids required to form dispersions of polydioxythiophenes and polyanions, mixtures of alkali metal salts of polyacids and corresponding amounts of monoacids may also be used.

The optionally present hole conductive layer is preferably adjacent to the hole injection layer, preferably at least one aromatic tertiary amino compound, preferably an optionally substituted triphenylamine compound, particularly preferably the tris- 1,3,5- (aminophenyl) benzene compound.

In the above formula,

R ⁷ is hydrogen, optionally substituted alkyl or halogen,

R ⁸ and R ⁹ are independently of each other optionally substituted (C ₁ -C ₁₀ ) -alkyl, preferably (C ₁ -C ₆ ) -alkyl, in particular methyl, ethyl, n-propyl or isopropyl, n-butyl , Isobutyl, sec-butyl or tert-butyl, alkoxycarbonyl-substituted (C ₁ -C ₁₀ ) -alkyl, preferably (C ₁ -C ₄ ) -alkoxycarbonyl- (C ₁ -C ₆ )- Alkyl, eg methoxy-, ethoxy-, propoxy- or butoxycarbonyl- (C ₁ -C ₄ ) -alkyl, each optionally substituted, aryl, aralkyl or cycloalkyl, preferably each optionally is (C ₁ -C ₄₎ - alkyl and (or) (C ₁ -C ₄₎ - alkoxy, phenyl substituted with a - (C ₁ -C ₄₎ - alkyl, naphthyl, - (C ₁ -C ₄₎ - Alkyl, cyclopentyl, cyclohexyl, phenyl or naphthyl.

Substituents optionally present in such radicals are to be understood to mean, for example, straight or branched alkyl, cycloalkyl, aryl, halogenoalkyl, halogen, alkoxy and sulfo radicals.

R ⁸ and R ⁹ independently of one another are particularly preferably unsubstituted phenyl or naphthyl, or methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and / or isopro, respectively Phenyl or naphthyl which is monosubstituted to trisubstituted by foxy.

R ⁷ is preferably hydrogen, (C ₁ -C ₆ ) -alkyl, for example methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or chlorine .

Such compounds and their preparation are described in US Pat. No. 4, 923,774 for use in electrophotography. Tris-nitrophenyl compounds can be converted to tris-aminophenyl compounds, for example by generally known catalytic hydrogenation in the presence of Raney nickel (Houben-Weyl 4 / 1C, 14-102, Ullmann ( 4) 13, 135-148]). The amino compound is reacted with a halogenated benzene substituted in a generally known manner.

In addition to the tertiary amino compounds, additional hole conductors may optionally be used to prepare the electroluminescent devices, for example in the form of mixtures with tertiary amino compounds. On the one hand they can be one or more compounds of the formula (K) in which a mixture of isomers is also included, and on the other hand it can also be a mixture of hole transport compounds of different structure than the tertiary amino compounds of the formula (K).

A list of possible hole injection and hole conducting materials is given in EP-A 0 532 798.

In the case of mixtures of aromatic amines, the compounds can be used in any desired proportions.

The optionally present electron transport layer is preferably adjacent to the light emitting layer, preferably Alq ₃ (q = 8-hydroxyquinolinato), Gaq ₃ , Al (qa) ₃ , Ga (qa) ₃ , or Ga (qa) ₂ OR ⁶ , Ga (qa) ₂ OCOR ⁶ or Ga (qa) ₂ -O-Ga (qa) ₂ , wherein R ⁶ is substituted or unsubstituted alkyl, aryl, arylalkyl or cycloalkyl And qa is Gallium complex from the group consisting of

The preparation of gallium complexes is described in European patent EP-A 949695 and German patent 19812258. The electron transport layer can be applied by vapor deposition (eg Alq ₃ ) or by applying the readily soluble gallium complex described from the solution, preferably by spin-coating, casting or knife-coating. Suitable solvents are, for example, methanol, ethanol, n-propanol or isopropanol.

In one specific embodiment, the electroluminescent device according to the present invention may contain a hole blocking layer between the light emitting layer and the electron transporting layer. Preferably, the hole blocking layer contains betocouproin (BCP) or TPBI (1,3,5-tris [N-phenylbenzimidazol-2-yl] benzene).

The electron injection layer is composed of an alkali metal fluoride or an alkali metal oxide or an organic compound n-doped by reaction with an alkali metal. The electron injection layer preferably contains LiF, Li ₂ O, Li quinolate and the like.

The layers or layers present between the hole injection layer and the cathode may also perform a number of functions. That is, one layer may contain, for example, hole injection, hole transport, electroluminescence (light emission), hole blocking, electron transport and / or electron injection materials.

The upper electrode can be composed of a conductive material that can be transparent. Preferably, metals that can be applied by techniques such as deposition, sputtering or platinum plating, for example Ca, Ba, Li, Sm, Al, Ag, Au, Mg, In, Sn, etc., or these Alloys of two or more metals are suitable.

Glass, very thin glass (flexible glass) or plastic is suitable as the transparent substrate on which the conductive layer is provided. Polycarbonates, polyesters, copolycarbonates, polysulfones, polyethersulfones, polyimides, polyethylenes, polypropylenes or cyclic polyolefins or cyclic olefin copolymers, hydrogenated styrene polymers or hydrogenated styrene copolymers are particularly suitable plastics .

One preferred embodiment of the present invention relates to an electroluminescent device wherein the electroluminescent device is a two-layer structure comprising a hole injection and light emitting layer.

One further preferred embodiment of the invention relates to an electroluminescent device in which the electroluminescent element is a one-layer structure comprising a light emitting layer.

In order to prevent decomposition, in particular decomposition by atmospheric oxygen and water, the device according to the invention can be encapsulated with a material having a high diffusion barrier to oxygen and water. Suitable materials include very thin glass (Schott Displayglass) and polymer lamination systems (SiO _x , Al ₂ O ₃ , MgO, Si _x N _y, etc.) that can be coated with metal oxides or metal nitrides by vapor deposition; Polyvinyl alcohol, Acla®, polyvinylidene difluoride, and the like.

In addition to the phosphorescent or light emitting polymers described in the present invention, the light emitting layer is a conductive polymer known to those skilled in the art to improve film forming properties, to control emission color and / or to affect charge carrier transport properties and ( Or) phosphorescent or luminescent polymers in blend form. Blend polymers are generally used in amounts of up to 95% by weight, preferably up to 80% by weight.

The electroluminescent device emits light at a wavelength of 200 to 2000 nm, preferably 400 to 800 nm upon application of a DC voltage in the range of 0.1 to 100 volts, preferably 1 to 100 volts. Additional emission in other spectral ranges is not excluded thereby, but does not affect the visually detectable color of the light emitted as a whole.

The electroluminescent device according to the invention is, for example, as a laser diode in an indicator or as a display (TV, computer monitor, etc.), for backlighting of LCDs and watches, as a lighting element in a flat light source, as a household appliance (for example Can be used as an indicator for a washing machine, a refrigerator, a vacuum cleaner, etc.), as a guide sign in a mobile communication device, or as an integrated display in a displacement system or the like.

The production of electroluminescent devices in electroluminescent devices is also in accordance with the invention, wherein phosphorescent or luminescent conjugated polymers are applied from solution.

To prepare the electroluminescent device, the phosphorescent or luminescent polymer is dissolved in a suitable solvent, preferably spin-coating, casting, dipping, knife-coating, screen printing, inkjet printing, flexographic printing or offset from the solution. Applies to substrates suitable for printing. Because of the faster process speeds and the smaller amount of waste generated, this method is substantially less costly, the process technique is simplified, and can be applied to a wider range of deposition methods for low molecular weight emitter materials. For example, compared to CVD). In particular, printing techniques enable targeted application of complex structures without expensive mask techniques and lithography processes.

Suitable solvents are alcohols, ketones, aromatic compounds, halogenated aromatic compounds, halogenated hydrocarbons and the like, or mixtures thereof. Preferred solvents are toluene, o- / m- / p-xylene, chlorobenzene, di- and trichlorobenzene, chloroform, THF and the like. The solution concentration of the phosphorescent or light emitting polymer is from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 0.5 to 3% by weight. The layer thickness of the light emitting layer is from 5 nm to 1 μm, preferably from 5 nm to 500 nm, particularly preferably from 20 nm to 500 nm and very particularly preferably from 20 nm to 100 nm.

The substrate can be, for example, a glass or plastic material provided with a transparent electrode. Plastic materials used are, for example, polycarbonates, polyesters such as polyethylene terephthalate or polyethylene naphthalate, copolycarbonates, polysulfones, polyethersulfones, polyimides, polyethylene, polypropylene or cyclic polyolefins. Or a film of a cyclic olefin copolymer, hydrogenated styrene polymer or hydrogenated styrene copolymer. The substrate may also be a layer device already containing one or more layers 1 to 10 (see page 2), preferably 1 to 7, which are included in the basic structure of the EL device, and one layer functions as a function of many of these layers. Can be performed.

Suitable transparent electrodes include metal oxides such as indium tin oxide (ITO), tin oxide (NESA), zinc oxide, doped tin oxide, doped zinc oxide and the like; Translucent metal films such as Au, Pt, Ag, Cu and the like; Conductive polymer films such as polythiophene, polyaniline and the like. The thickness of the transparent electrode is 3 nm to about several μm, preferably 10 nm to 500 nm.

Claims (29)

A phosphorescent polymer containing at least one covalently bonded phosphorescent metal complex, which is conjugated and neutral. The phosphorescent conjugated polymer of claim 1, wherein the phosphorescent conjugate polymer contains at least one phosphorescent metal complex covalently bonded by at least one ligand L ¹ which is a unit of Formulas I to XXIX: In the above formula, R is the same or different and independently from each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and consisting of nitrogen, oxygen and sulfur, substituted with C ₅ -C ₂₀ -aryl units substituted with —alkyl and / or optionally C ₁ -C ₃₀ -alkyl A heteroaryl unit having 1 to 3 atoms in the ring, Ar is an optionally substituted phenylene, biphenylene, naphthylene, thienylene and fluorenylene unit. The phosphorescent conjugated polymer according to claim 1 or 2, wherein the phosphorescent conjugate polymer contains a repeating unit of Formulas A and B-Ia or A and B-II or has a structure of Formula C or D: In the above formula, Ar ¹ , Ar ² and Ar ³ are the same or different and independently of one another are C ₅ -C ₂₀ -aryl units optionally substituted with C ₁ -C ₃₀ -alkyl and / or optionally C ₁ -C _30- A heteroaryl unit having 5 to 9 carbon atoms in the ring, substituted with alkyl, and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen, and sulfur, L ¹ and L ² are the same or different, L ¹ has one of the meanings set forth in claim 2, wherein for structures B-II, C and D one of the two linking positions is H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, linear or branched C ₁ -C ₂₂ - alkoxy groups, optionally C ₁ -C ₃₀ - alkyl substituted by C ₅ -C ₂₀ - aryl units, and (or) optionally at least one C ₁ -C ₃₀ -, the ring substituted with alkyl Saturated with heteroaryl units having from 5 to 9 carbon atoms in the group and from 1 to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, L ² is L ¹ and are independently as one of the means described in claim 2 for the L ^1, two of the connection location is independently selected from H, F, CF _3, linear or branched one another C ₁ -C ₂₂ - alkyl, Linear or branched C ₁ -C ₂₂ -alkoxy groups, optionally substituted with C ₅ -C ₂₀ -aryl units substituted with C ₁ -C ₃₀ -alkyl, and / or optionally substituted with C ₁ -C ₃₀ -alkyl, Saturated with heteroaryl units having from 5 to 9 carbon atoms in the ring and from 1 to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, Ligands L ¹ and L ² complex the metal M in a chelate-like manner, M is iridium (III), platinum (II), osmium (II) or gallium (III), n is an integer from 3 to 10000, z is an integer from 0 to 3, Sp is a spacer, in particular a linear or branched C ₂ -C ₁₅ - alkylene-heteroaryl units - alkylene unit, or C ₂ -C ₁₅ with 1 to 3 hetero atoms in the chain, from the group consisting of nitrogen, oxygen and sulfur , A C ₅ -C ₂₀ -arylene unit and / or a heteroarylene unit having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, or C ₁ -C ₁₂ -alkylenecarboxylic acid unit or C ₁ -C ₁₂ -alkylenedicarboxylic acid unit or C ₁ -C ₁₂ -alkylenecarboxamide unit or C ₁ -C ₁₂ -alkylenedicarboxamide Unit. The thiophene units of the formulas XXX and XXXI, benzene of the formulas XXXII to XXXIV, according to any one of claims 1 to 3, wherein Ar ¹ , Ar ² and Ar ³ are the same or different and independently of each other; A phenyl and fluorene unit and / or a repeating unit of formula A and B-Ia or A and B-II, or a structure of formula C or D, which is a heterocycle of the formulas XXXV to XXXXXIV Phosphorescent Conjugated Polymer: In the above formula, R is the same or different and is independently of each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and consisting of nitrogen, oxygen and sulfur, substituted with C ₅ -C ₂₀ -aryl units substituted with —alkyl and / or optionally C ₁ -C ₃₀ -alkyl Heteroaryl units having 1 to 3 atoms in the ring. The benzene according to any one of claims 1 to 4, wherein Ar ¹ , Ar ² and Ar ³ are the same or different and independently of each other, and thiophene units of the following formulas XXX and XXXI and benzene of the following formulas XXXII to XXXIV Phenyl and fluorene units, L ¹ and L ² are units selected from the following formulas I, II, III, VIII, XVIII, XX, XXI, XXIV, XXVII, XXVIII and XXIX, M osmium (II), iridium ( III) and platinum (II), n is an integer from 5 to 500, z is an integer from 1 to 3, Sp is C ₁ -C ₆ -alkyleneoxy- or C ₁ -C ₆ -alkylenecarboxyl A phosphorescent conjugated polymer containing a repeating unit of Formulas A and B-Ia or A and B-II or having a structure of Formula C or D, which is an acid or C ₁ -C ₆ -alkylenedicarboxylic acid: In the above formula, R has the meaning as described in any one of Claims 2-4. The compound according to any one of claims 1 to 5, containing a repeating unit selected from formulas A and BI-1 to BI-5 or A and B-II-1 and B-II-4 or A phosphorescent conjugated polymer having the structure of -1 and C-2: In the above formula, Ar ¹ is ego, Ar ² is ego, L is ego, R ¹ is dodecyl, R ² is n-octyl and 2-ethylhexyl, R ³ is methyl and ethyl, R ⁴ is methyl and n-hexyl, R ⁵ is methyl and phenyl, Z is a CH ₂ or C═O group, n is at least one of the meanings as described in any one of Claims 3-5. The phosphorescent conjugated polymer of claim 1, wherein the phosphorescent conjugate polymer contains at least one phosphorescent metal complex covalently bonded through at least one ligand L ¹ which is a unit of Formulas I to XXIXc: In the above formula, R is the same or different and independently from each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and substituted with nitrogen, oxygen and sulfur, substituted with a C ₅ -C ₂₀ -aryl unit and / or optionally substituted with C ₁ -C ₃₀ -alkyl substituted with an alkyl A heteroaryl unit having 1 to 3 atoms in the ring, and / or a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group , A nitro group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group, or an alkyl- or arylcarbonyl group, wherein alkyl is C ₁ -C ₃₀ -alkyl and aryl is C ₅ -C ₂₀ -aryl), Ar is an optionally substituted phenylene, biphenylene, naphthylene, thienylene and / or fluorenylene unit. 8. A compound according to any one of claims 1 to 7, containing repeating units of the formulas A and B-Ia, A and B-Ib or A and B-II or having the structure of the following formulas C or D Phosphorescent conjugated polymer characterized by: In the above formula, Ar ¹ , Ar ² and Ar ³ are the same or different and independently of one another are C ₅ -C ₂₀ -aryl units optionally substituted with C ₁ -C ₃₀ -alkyl and / or optionally C ₁ -C _30- A heteroaryl unit having 5 to 9 carbon atoms in the ring substituted by alkyl and having 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, L ¹ and L ² are the same or different, L ¹ has ^one of the above meanings, and for structures B-II, C and D one of the two linking positions is H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, linear or branched A carbon atom in the ring substituted with a C ₅ -C ₂₀ -aryl unit optionally substituted with a C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ -alkyl, and / or optionally substituted with a C ₁ -C ₃₀ -alkyl Saturated or linear or branched partial fluorinated or perfluorinated C ₁ -C by heteroaryl units having 5 to 9 heteroatoms from the group consisting of nitrogen, oxygen and sulfur and 1 to 3 in the ring Saturated by a ₂₂ -alkyl group, linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group, nitro group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group or alkylarylamino group, or alkyl- Or an arylcarbonyl group wherein alkyl is C ₁ -C ₃₀ -alkyl Aryl is saturated) and C ₅ -C ₂₀ -aryl L ² is independently from ¹ and L is one of the aforementioned means for the L ^1, the two connection positions, independently of each other H, F, CF _3, linear or branched C ₁ -C ₂₂ - alkyl group, a linear or branched C ₁ -C ₂₂ - alkoxy groups, optionally C ₁ -C ₃₀ - alkyl substituted by C ₅ -C ₂₀ - aryl units, and (or) optionally at least one C ₁ -C ₃₀ -, the carbon in the ring substituted with alkyl Saturated or saturated or linear or branched partial fluorinated or perfluorinated C ₁ -heteroaryl units having from 5 to 9 atoms and having from 1 to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur; C ₂₂ - alkyl group, a linear or branched C ₁ -C ₂₂ - alkoxycarbonyl group, a cyano group, a nitro group, an amino group, alkylamino group, dialkylamino group, arylamino group, or a saturated by the diarylamino group, or an alkylaryl group, or an alkyl Or an arylcarbonyl group, wherein alkyl C ₁ -C ₃₀ -alkyl and aryl is C ₅ -C ₂₀ -aryl) The linking position should be understood to mean the position indicated by * in Formulas I to XXIX, Ligands L ¹ and L ² complex the metal M in a chelate-like manner, M is iridium (III), platinum (II), osmium (II), gallium (III) or rhodium (III), n is an integer from 3 to 10000, z is an integer from 0 to 3, Sp is a spacer, in particular a linear or branched C ₂ -C ₁₅ - alkylene-heteroaryl units - alkylene unit, or C ₂ -C ₁₅ with 1 to 3 hetero atoms in the chain, from the group consisting of nitrogen, oxygen and sulfur , A C ₅ -C ₂₀ -arylene unit and / or a heteroarylene unit having 5 to 9 carbon atoms in the ring and 1 to 3 heteroatoms in the ring from the group consisting of nitrogen, oxygen and sulfur, or C ₁ -C ₁₂ -alkylenecarboxylic acid unit or C ₁ -C ₁₂ -alkylenedicarboxylic acid unit or C ₁ -C ₁₂ -alkylenecarboxamide unit or C ₁ -C ₁₂ -alkylenedicarboxamide Unit. The thiophene according to any one of claims ¹ , 7 and 8, wherein Ar ¹ , Ar ² and Ar ³ are the same or different and independently of each other, Benzene, biphenyl and fluorene units, and / or Formulas A and B-Ia, A and B-Ib or A and B, which are heterocycles of the formulas XXXV to XXXXXIV and / or units of the formulas XXXXXV to XXXXXXIII A phosphorescent conjugated polymer containing a repeating unit of -II or having a structure of formula C or D: In the above formula, R is the same or different and independently from each other H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxy group, optionally C ₁ -C ₃₀ Hetero from the group consisting of 5 to 9 carbon atoms in the ring and substituted with nitrogen, oxygen and sulfur, substituted with a C ₅ -C ₂₀ -aryl unit and / or optionally substituted with C ₁ -C ₃₀ -alkyl substituted with an alkyl A heteroaryl unit having 1 to 3 atoms in the ring, and / or a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, a linear or branched C ₁ -C ₂₂ -alkoxycarbonyl group, cyano group , A nitro group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group, or an alkyl- or arylcarbonyl group, wherein alkyl is C ₁ -C ₃₀ -alkyl and aryl is C ₅ -C ₂₀ -aryl). The compound according to any one of claims 1 and 7 to 9, containing a repeating unit selected from the formulas A and BI-1 to BI-6 or A and B-II-1 to B-II-4. Or a phosphorescent conjugated polymer having the structure of Formula C-1, C-2 or C-3 or D-1, D-2 or D-3: In the above formula, Ar ¹ is ego, Ar ² is ego, L is ego, R ¹ is dodecyl, R ² is n-octyl and 2-ethylhexyl, R ³ is methyl and ethyl, R ⁴ is methyl and n-hexyl, R ⁵ is methyl and phenyl, R ⁶ is H, a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched C ₁ -C ₂₂ -alkoxy group, Z is a CH ₂ or C═O group, n has the meaning described in Claim 8. A light emitting polymer having a conjugated backbone, containing one or more covalently bonded metal complexes, wherein the luminescence is a combination of fluorescence of the conjugated backbone and phosphorescence of the covalently bonded metal complexes or complexes. The light emitting polymer of claim 11, wherein the light emitting polymer emits white light. 13. The light emitting polymer according to claim 11 or 12, which emits light defined by the color position of x = 0.33 ± 0.13 and y = 0.33 ± 0.13 in a chromaticity diagram according to CIE 1931. The light emitting polymer according to any one of claims 11 to 13, wherein the same or different metal complexes or complexes are covalently bonded to the chain ends of the conjugated backbone. A light emitting polymer according to claim 14 having the structure of formula (la) or (lb): In the above formula, Ar ¹ is optionally substituted with the following phenylene units (IIa) or (IIb), biphenylene units (IIc), fluorenylene units (IId), dihydroindenofluorenylene units (IIe), spirobifluores Nylene units (IIf), dihydrophenanthrylene units (IIg) or tetrahydropyrenylene units (IIh), Ar ² is different from Ar ¹ and is a unit selected from the following formulas (IIa) to (IIq), L ¹ and L ² are the same or different at each occurrence, L ¹ is a ligand of formulas (IIIa-1) to (IIId-1), Ar is an optionally substituted phenylene, biphenylene, naphthylene, thienylene or fluorenylene unit, L ² is L ¹ and is in the following as a ligand selected from units of the formula (IVa-1) to (IVy-1) independent of the ligand L ¹ and L ² and is complexed with the metal M chelate similar manner, M is iridium (III), platinum (II), osmium (II) or rhodium (III), n is an integer from 3 to 10000, z is an integer from 1 to 3, R is the same or different radicals and, independently of one another, H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, Linear or branched C ₁ -C ₂₂ -alkoxy groups, optionally substituted with C ₅ -C ₂₀ -aryl units substituted with C ₁ -C ₃₀ -alkyl, and / or optionally substituted with C ₁ -C ₃₀ -alkyl, Heteroaryl units having from 5 to 9 carbon atoms in the ring and from 1 to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur. The light emitting polymer according to claim 14 or 15, which has a structure represented by the following formulas (Ia-1) to (Ib-2): In the above formula, R is a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched partially fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, n, Ar ¹ , Ar ² and L ² have the meaning described in claim 15. The light emitting polymer according to claim 14 or 15, which has a structure of formula (Ia-3) or (Ib-3): In the above formula, R is a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched partially fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, n, Ar ¹ , Ar ² and L ² have the meaning described in claim 15. The light emitting polymer according to any one of claims 11 to 13, wherein the same or different metal complexes or complexes are covalently bonded to the conjugated backbone. The light emitting polymer according to claim 18, which contains n repeating units represented by the following formulas (Ic-1) and (Id) or (Ic-1), (Ic-2) and (Id): In the above formula, Ar ¹ is optionally substituted with the following phenylene units (IIa) or (IIb), biphenylene units (IIc), fluorenylene units (IId), dihydroindenofluorenylene units (IIe), spirobifluores Nylene units (IIf), dihydrophenanthrylene units (IIg) or tetrahydropyrenylene units (IIh), Ar ² is different from Ar ¹ and is a unit selected from the following formulas (IIa) to (IIq), L ¹ and L ² are the same or different at each occurrence, L ¹ is a ligand of formulas (IIIa-2) to (IIIi-1) L ² is L ¹ and is in the following as a ligand selected from units of the formula (IVa-1) to (IVy-1) independent of the ligand L ¹ and L ² and is complexed with the metal M chelate similar manner, M is iridium (III), platinum (II), osmium (II) or rhodium (III), n is an integer from 3 to 10000, z is an integer from 1 to 3, R is the same or different radicals and, independently of one another, H, F, CF ₃ , a linear or branched C ₁ -C ₂₂ -alkyl group, a linear or branched partial fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, Linear or branched C ₁ -C ₂₂ -alkoxy groups, optionally substituted with C ₅ -C ₂₀ -aryl units substituted with C ₁ -C ₃₀ -alkyl, and / or optionally substituted with C ₁ -C ₃₀ -alkyl, Heteroaryl units having from 5 to 9 carbon atoms in the ring and from 1 to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur. 20. A light emitting polymer according to claim 19, which contains n repeating units of formulas (Ic-1) and (Id-1): In the above formula, R is a linear or branched C ₁ -C ₂₂ -alkyl group or a linear or branched partially fluorinated or perfluorinated C ₁ -C ₂₂ -alkyl group, n, Ar ¹ and L ² have the meaning described in claim 18. The light emitting polymer according to any one of claims 15 to 20, wherein L ² is a ligand selected from units of the formula: 22. The light emitting polymer according to any one of claims 15 to 21, wherein Ar ¹ and Ar ² are independently of each other a unit of the formula: In the above formula, R is a linear or branched C ₁ -C ₂₂ -alkyl group. The light emitting polymer according to any one of claims 15 to 22, wherein n is an integer from 10 to 5000, preferably from 20 to 1000, particularly preferably from 40 to 500. The phosphorescent or luminescent light according to any one of claims 1 to 23, wherein the uncomplexed ligand polymer is complexed with an iridium (III), platinum (II), osmium (II) or rhodium (III) precursor complex. Method of Making Polymers. 25. The process of claim 24, wherein the uncomplexed ligand polymer is complexed with an iridium (III) precursor complex of formula E. In said formula, L <^2> has the meaning as described in any one of Claims 1-23. Use of the phosphorescent or luminescent polymer according to any one of claims 1 to 23 or a blend thereof as an emitter in the light emitting component. An electroluminescent device comprising at least one phosphorescent or light emitting polymer according to any one of claims 1 to 23 or a blend thereof. 28. An electroluminescent device according to claim 27, comprising a hole injection layer. A method for producing an electroluminescent element in an electroluminescent device according to claim 27 or 28, wherein the phosphorescent or light emitting polymer according to any one of claims 1 to 23 or a blend thereof is applied from a solution.