Organic electronic material

Abstract

The present invention discloses an organic electronic material, belonging to the organic light-emitting device (OLED) display materials field. The organic electronic material in the present invention has a structural formula (I), having good thermal stability, high luminous efficiency, high purity of light emission. The OLED made by this kind of organic light-emitting material has the advantages of excellent organic light-emitting efficiency, excellent color purity and long service life. ##STR00001##

Claims

1. An organic electronic material comprising the following structural formula (I): ##STR00037## Wherein R.sub.1-R.sub.17 independently represent hydrogen, halogen, cyano, nitro, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, C.sub.2-C.sub.8 substituted or unsubstituted alkenyl, C.sub.2-C.sub.8 substituted or an unsubstituted alkynyl, C.sub.1-C.sub.4 alkyl substituted or unsubstituted phenyl, C.sub.1-C.sub.4 alkyl substituted or unsubstituted naphthyl, or combined C.sub.1-C.sub.4 alkyl substituted or unsubstituted fluorenyl; and Ar.sub.1-Ar.sub.3 independently represent C.sub.1-C.sub.4 alkyl substituted phenyl, phenyl, pyridyl.

2. The organic electronic material according to claim 1, wherein R.sub.1-R.sub.2 independently and preferably represent hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkyl substituted or unsubstituted phenyl, C.sub.1-C.sub.4 alkyl substituted or unsubstituted naphthyl, or combined C.sub.1-C.sub.4 alkyl-substituted or unsubstituted fluorenyl; and R.sub.3-R.sub.17 may independently represent hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkyl substituted or unsubstituted phenyl, C.sub.1-C.sub.4 alkyl-substituted or unsubstituted naphthyl, preferably Ar.sub.1-Ar.sub.3 independently represent phenyl, tolyl, xylyl, t-butylphenyl.

3. The organic electronic material according to claim 2, wherein R.sub.3-R.sub.17 preferably represents hydrogen, and R.sub.1 and R.sub.2 may independently represent hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, biphenyl, naphthyl, or combined fluorenyl; Ar.sub.1-Ar.sub.3 may independently represent phenyl, pyridyl, tolyl, xylyl.

4. The organic electronic material according to claim 3, wherein R.sub.3-R.sub.17 represent hydrogen preferably; R.sub.1, R.sub.2 independently represent hydrogen, methyl or combined fluorenyl; and Ar.sub.1, Ar.sub.2, Ar.sub.3 independently represent phenyl.

5. The organic electronic material according to claim 1, wherein its structure is as follows: ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067##

6. The organic electronic material according to claim 5, wherein its structure is as follows: ##STR00068##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a structural charge of the device, of which, 10 denotes a glass substrate, 20 denotes an anode, 30 denotes hole injection layer, 40 denotes hole transport layer, 50 denotes light emitting layer, 60 denotes electron transport layer, 70 denotes electron injection layer, 80 denotes cathode.

(2) FIG. 2 is the .sup.1H NMR diagram of compound 89.

(3) FIG. 3 is the .sup.13C NMR diagram of compound 89.

(4) FIG. 5 is the TGA map of compound 89.

(5) FIG. 6 shows the voltage-current density curves of Embodiments 4 and 5 and Comparative Example 1.

(6) FIG. 7 shows the brightness CIEy plot of Embodiments 4 and 5 and Comparative Example 1.

(7) FIG. 8 shows the light-emitting spectra of Embodiments 4 and 5 and Comparative Example 1.

(8) FIG. 9 shows the current density-current efficiency curves of Embodiments 4 and 5 and Comparative Example 1.

DETAILED DESCRIPTIONS OF THE PREFERRED EMBODIMENTS

(9) In the following, the present invention is described in details by combining the following examples.

(10) (The compounds 1a, 1b, 1e, 1h, 3a, 89a are common materials available in the markets)

Embodiment 1

(11) ##STR00031## ##STR00032##
Synthesis of Intermediate 1c

(12) Add 1a (240.00 g, 0.88 mol), 1b (496.32 g, 1.76 mol), Pd(PPh.sub.3).sub.4 (20.35 g, 17.60 mmol), potassium carbonate (302.52 g, 2.20 mol), toluene (2400 mL), pure water (1200 mL) to a reaction flask. Start to heat after extracting air for three times, and when the reaction solution temperature reaches 95-105V, maintain it for 8-12 h; take samples for TLC and HPLC, to completely react. Stop heating and cool down to 20-30 C., perform suction filtration to separate the organic layer from filtrate. Extract the aqueous layer with ethyl acetate, combine the organic layer, then wash with water, dry by anhydrous magnesium sulfate, and perform suction filtration, to get the filtrate. Concentrate the filtrate to get a dark yellow solid crude product. The crude product is recrystallized from petroleum ether to get an off-white solid product, with a yield of 90% and a purity of 95%.

(13) Synthesis of Intermediate 1d

(14) Add 1c (302 g, 0.78 mol), B(OEt).sub.3 (142 g, 0.97 mol), n-BuLi/THF (1.6 M, 600 mL), and anhydrous THF (3000 mL) at appropriate ratio to a reaction flask. After extracting with nitrogen for three times, cool down until the reaction solution temperature is 7565 C., slowly add n-BuLi/THF solution dropwise and control the temperature at 7565 C.; after dripping, continue to maintain this temperature for reaction 0.5-1 h. Then add appropriate amount of B(OEt).sub.3 dropwise, to control the reaction solution temperature at 7565 C., after dripping, continue to maintain this temperature for reaction 0.5-1 h. Then transfer the solution to room temperature for naturally heating reaction 4-6 h, then add 2M dilute hydrochloric acid to adjust the PH value to 2-3, after stirring about 1 h, stop the reaction. Add ethyl acetate to extract the solution, and the aqueous layer is extracted by EA. The organic layers are combined and dried over anhydrous magnesium sulfate, then suction filtration is conducted. The filtrate is concentrated to get an off-white solid product, with a purity of 95% and a yield of 62.5%.

(15) Synthesis of Intermediate 1f

(16) Add 1d (150 g, 0.43 mol), 1e (500 g, 0.86 mol), Pd(PPh.sub.3).sub.4 (5.0 g, 0.44 mmol), potassium carbonate (130 g, 0.92 mol), toluene (1000 mL), pure water (500 mL) to a reaction flask. Start to heat after extracting nitrogen for three times, and when the reaction solution temperature reaches 95-105 C., maintain it for 8-12 h; take samples for TLC and HPLC, to completely react. Stop heating and cool down to 20-30 C., perform suction filtration to separate the organic layer from filtrate. Extract the aqueous layer with ethyl acetate, combine the organic layers, dry by anhydrous magnesium sulfate, and perform suction filtration. The filtrate is concentrated to get dark yellow solid crude product, with a purity of 80% and a yield of 78.1%.

(17) Synthesis of Intermediate 1g

(18) Add 1f (210 g, 0.42 mol), NBS (135 g, 0.71 mol), DMF (5 L) to a reaction flask. Start to heat after extracting nitrogen for three times, and when the reaction solution temperature reaches 60-65 C., maintain it for 6-8 h; take samples for TLC and HPLC, to completely react. Stop heating and cool down to 20-30 C., then pour the reaction solution to ice-water to separate dark yellow solid, and then perform suction filtration to get yellow solid and bake to obtain 1 g of crude product. Add the crude product to DCM/MeOH until the solution becomes slightly turbid, continue to stir for about 30 min, to separate out a large amount of solid, then perform suction filtration to get pale yellow solid product, with a yield of approximate 54.05% and a purity of 98.5%.

(19) .sup.1H NMR (300 MHz, CDCl.sub.3) 8.64 (d, J=8.8 Hz, 2H), 7.99-7.90 (m, 4H), 7.87 (t, J=1.6 Hz, 1H), 7.78 (dd, J=9.3, 2.3 Hz, 6H), 7.61 (ddd, J=8.8, 6.5, 1.1 Hz, 2H), 7.56-7.48 (m, 6H), 7.46-7.38 (m, 4H).

(20) .sup.13C NMR (76 MHz, CDCl.sub.3) 142.67 (s), 142.03 (s), 141.26 (s), 140.69 (s), 137.83 (s), 137.52 (s), 131.87 (s), 131.24 (s), 130.44 (s), 129.09 (s), 128.80 (s), 128.38-127.40 (m), 127.18 (s), 126.05-125.21 (m), 123.08 (s), 77.74 (s), 77.31 (s), 76.89 (s), 30.10 (s).

(21) Synthesis of Compound 1

(22) Add 1 g (9.5 g, 16.92 mmol), 1h (6.41 g, 30.51 mmol), Pd(PPh.sub.3).sub.4 (1.5 g, 1.3 mmol), potassium carbonate (5.84 g, 42.3 mmol), toluene (150 mL) and pure water (75 mL) to a 500 ml three-necked flask. After extracting nitrogen for three times, reaction occurs at 105 C. The time of reaction stop is around 12 h, which is detected by liquid phase. The reaction solution is earth yellow of catalyst at the beginning, slowly turning into a yellow solution. After reaction stops, the upper layer is bright and light yellow, and the lower layer is water. After reaction stops, filter the solution, wash the filter residues with ethyl acetate until no product in the residue, then collect the filtrate, spin-dry, to separate out a large amount of off white solid. Collect the filter residue to dry, to get the target product, with purity of 98%; after vacuum sublimation, gray-white solid powder with purity of 99.5% is obtained.

(23) .sup.1H-NMR (300 MHz, CDCl.sub.3) 8.10-8.21 (d, 2H), 7.96-7.98 (dd, 3H), 7.87-7.89 (m, 2H), 7.81-7.86 (m, 4H), 7.78-7.81 (d, 4H), 7.62-7.65 (m, 2H), 7.59 (s, 1H), 7.51-7.57 (m, 5H), 7.45-7.48 (m, 2H), 7.36-7.43 (m, 7H), 3.88 (s, 2H).

Embodiment 2

(24) Synthesis of Compound 3

(25) ##STR00033##

(26) Add 1 g (9.5 g, 16.92 mmol), 3a (7.25 g, 30.46 mmol), Pd(PPh.sub.3).sub.4 (1.5 g, 1.3 mmol), potassium carbonate (5.84 g, 42.3 mmol), toluene (150 mL) and pure water (75 mL) to a 500 ml three-necked flask. After extracting nitrogen for three times, reaction occurs at 105 C. The time of reaction stop is around 12 h, which is detected by liquid phase.

(27) The reaction solution is earth yellow of catalyst at the beginning, slowly turning into a yellow solution. After reaction stops, the upper layer is bright and light yellow, and the lower layer is water. After reaction stops, filter the solution, wash the filter residues with ethyl acetate until no product in the residue, then collect the filtrate, spin-dry, to separate out a large amount of off white solid. Collect the filter residue to dry, to get the target product, with purity of 98%; after vacuum sublimation, gray-white solid powder with purity of 99.7% is obtained.

(28) .sup.1H-NMR (300 MHz, CDCl.sub.3) 8.1-8.2 (d, 2H), 7.96-7.99 (dd, 3H), 7.88-7.89 (m, 2H), 7.81-7.86 (m, 4H), 7.78-7.81 (d, 4H), 7.61-7.65 (m, 2H), 7.59 (s, 1H), 7.51-7.56 (m, 5H), 7.46-7.48 (m, 2H), 7.35-7.43 (m, 7H), 1.61 (s, 6H).

Embodiment 3

(29) Synthesis of Compound 89

(30) ##STR00034##

(31) Add 1 g (10.0 g, 17.8 mmol), 89a (7.1 g, 19.6 mmol), Pd(PPh.sub.3).sub.4 (432.2 mg, 0.35 mmol), K2CO3 (6.14 g, 44.5 mmol), toluene (300 mL) and water (150 mL) successively to a reaction tank. After deoxygenization of the device and introduction of nitrogen, heat to 100 C. for reaction overnight, apply to the plates at a ratio of DCM:PE=1:5. The product gives out intensive blue light under UV light at 365 nm wavelength, with the Rf value at about 0.2. Perform suction filtration with the reaction solution, wash the filter cake with ethyl acetate (100 mL) twice and separate. Extract the aqueous layer with ethyl acetate (100 mL) once, combine the organic layers, then wash the organic layer once with water (200 mL). spin dry to remove the solvent. The crude product is recrystallized from 120 ml DCM/MeOH, then suction filtration is performed to get 13.1 g yellow solid powder, with a purity of 98.7% and a yield of 92.2% yield. After vacuum sublimation, a slight yellow solid powder with purity of 99.7% is obtained. m/z=797.

(32) As shown from FIG. 2 and FIG. 3, the hydrogen spectra and carbon spectra of compound 89 are completely consistent with the structures. From the high performance liquid chromatogram of compound 89 in FIG. 4, the product made by the synthesis method in the invention has high purity. According to the thermal gravametric analysis of compound 89 in FIG. 5, the decomposition temperature of this type of compound is higher than 400 degrees centigrade, indicating that it has very high thermal stability.

Embodiment 4

(33) Preparation of OLED1

(34) Prepare OLED by the Organic Electronic Material in the Present Invention

(35) Firstly, the ITO transparent conductive glass substrate 10 (with anode 20 above) is washed with detergent solution and deionized water, ethanol, acetone, deionized water in sequence, then treated with oxygen plasma for 30 seconds.

(36) Then, perform vacuum evaporation of 10 nm HAT-CN.sub.6 in ITO, which is used as the hole injection layer 30.

(37) Then, perform vacuum evaporation of NPB, to form 30 nm thick of hole transport layer 40.

(38) Then, perform vacuum evaporation of 30 nm thick of compound 3 in hole transport layer, which is used as light emitting layer 50.

(39) And then, perform vacuum evaporation of 15 nm thick of TPBi in light emitting layer, which is used as electron transport layer 60.

(40) Finally, perform vacuum evaporation of 15 nm BPhen:Li as electron injection layer 70, and vacuum evaporation of 150 nm Al as the device cathode 80.

(41) The voltage of the device made in 20 mA/cm2 of operating current density is 3.58 V, the current efficiency is 3.21 cd/A. The CIEy at the luminance of 1000 cd/m2 is 0.0853. It emits blue light.

(42) The Said Structural Formula of the Device

(43) ##STR00035##

Embodiment 5

(44) Preparation of OLED2

(45) Procedures are the same as Embodiment 4. OLED is made using compound 89 instead of compound 3 The voltage of the device made in 20 mA/cm2 of operating current density is 3.84 V, the current efficiency is 2.83 cd/A. The CIEy at the luminance of 1000 cd/m2 is 0.0888. It emits blue light.

Comparative Example 1

(46) The procedures are the same as Embodiment 4. OLED is made using the following compound TAT instead of compound 3, for comparison.

(47) TAT Structural Formula

(48) ##STR00036##

(49) The voltage of the device made in 20 mA/cm2 of operating current density is 4.00 V, the current efficiency is 2.46 cd/A. The CIEy at the luminance of 1000 cd/m2 is 0.0952. It emits blue light.

(50) The embodiments 4 and 5 are the specific applications of the material in the present invention. The blue light-emitting, efficiency and luminance of the devices are higher than those in the comparison example. Therefore, as stated above, the material in the present invention has high stability, and the OLED made in the invention has high efficiency and light purity.