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). The OLED made by this kind of organic light-emitting material has the advantages of excellent light-emitting efficiency, excellent color purity and long service lifetime. ##STR00001##

Claims

1. An organic electronic material having a structure of formula I: ##STR00042## wherein, R.sub.1-R.sub.8 independently represent hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C2-C8 substituted or unsubstituted alkenyl, C2-C8 substituted or unsubstituted alkynyl, C1-C4 alkyl substituted or unsubstituted phenyl, or C1-C4 alkyl substituted or unsubstituted naphthyl; and Ar.sub.1-Ar.sub.4 independently represent C1-C4 alkyl or C6-C30 aryl substituted phenyl, C1-C4 alkyl or C6-C30 aryl substituted naphthyl, phenyl, naphthyl, C6-C30 N-aryl or C1-C4 alkyl-substituted carbazolyl, dibenzothiophenyl, dibenzofuranyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthenyl, (9,9-di-alkyl) fluorenyl, (9,9-dialkyl-substituted or unsubstituted aryl) fluorenyl, or 9,9-spiro-fluorenyl.

2. The organic electronic material according to claim 1, wherein: R.sub.1-R.sub.8 independently represent hydrogen, halogen, C1-C4 alkyl, C1-C4 alkyl substituted or unsubstituted phenyl, or C1-C4 alkyl substituted or unsubstituted naphthyl; and Ar.sub.1-Ar.sub.4 independently represent phenyl, tolyl, t-butyl phenyl, naphthyl, methyl naphthalene, biphenyl, diphenyl phenyl, naphthyl phenyl, diphenyl-biphenyl, biaryl amine phenyl, N-phenyl-carbazolyl, (9,9-di-alkyl) fluorenyl, (9,9-dialkyl-substituted or unsubstituted phenyl) fluorenyl, or 9,9-spiro-fluorenyl.

3. The organic electronic material according to claim 2, wherein, R.sub.1, R.sub.4, R.sub.5, and R.sub.8 are hydrogen, R.sub.2, R.sub.3, R.sub.6, and R.sub.7 independently represent hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, or naphthyl; and Ar.sub.1-Ar.sub.4 independently represent phenyl, tolyl, naphthyl, methyl naphthyl, biphenyl, diphenyl phenyl, naphthyl phenyl, diphenyl-biphenyl, (9,9-di-alkyl) fluorenyl, (9,9-dimethyl-substituted or unsubstituted phenyl) fluorenyl, or 9,9-spiro-fluorenyl.

4. The organic electronic material according to claim 3, wherein: Ar.sub.2, Ar.sub.3, and Ar.sub.4 independently represent phenyl, naphthyl, or biphenyl, and Ar.sub.1 is phenyl, naphthyl, biphenyl, diphenyl phenyl, naphthyl phenyl, diphenyl-biphenyl, (9,9-di-alkyl) fluorenyl, (9-tolyl, 9-phenyl) fluorenyl, or 9,9-spiro-fluorenyl.

5. The organic electronic material according to claim 4, wherein: R.sub.2, R.sub.3, R.sub.6, and R.sub.7 are hydrogen, and Ar.sub.2, Ar.sub.3, and Ar.sub.4 independently represent phenyl or naphthyl.

6. An organic electronic material having a structure of one of the following structures: ##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## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081##

7. The organic electronic material according to claim 6, wherein the structure is one of the following structures: ##STR00082##

8. The organic electronic material of claim 1, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

9. The organic electronic material of claim 2, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

10. The organic electronic material of claim 3, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

11. The organic electronic material of claim 4, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

12. The organic electronic material of claim 5, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

13. The organic electronic material of claim 6, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

14. The organic electronic material of claim 7, wherein the structure is in an organic light-emitting device, organic solar cell, organic thin-film transistor, or organic photoreceptor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIG. 2 is the .sup.1H NMR spectrum of compound 110.

DETAILED DESCRIPTIONS OF THE PREFERRED EMBODIMENTS

(3) In the following, the present invention is described in details by giving the following examples.

Embodiment 1

(4) Synthesis of Compound 110

(5) ##STR00037## ##STR00038##

(6) Synthesis of Intermediate 1-1

(7) To a 1 L single-necked flask, was added 25.5 g 1-naphthaleneboronic acid and 25 g bromobenzaldehyde, 400 ml dioxane, 80 ml 2 M potassium carbonate solution, 1.0 g tetrakis(triphenylphosphine)palladium under the protection of nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, concentrated, and recrystallized from ethanol to yield 29 g solid (92%).

(8) Synthesis of Intermediate 1-3

(9) To a 500 ml single-neck flask, was added 25 g p-bromobenzyl bromide and 49.8 ml triethyl phosphite (1-2). The mixture was refluxed for 2 hours, then the excess triethyl phosphate was removed. 23.4 g intermediate 1-1, 250 ml DMF, and 16.8 g potassium tert-butoxide were added into the flask in an ice bath. The resulting mixture was allowed to warm to the room temperature, and stirred overnight. The reaction mixture was poured into distilled water, filtered, and the precipitate was recrystallized from ethanol to yield 31.8 g product (83%).

(10) Synthesis of Intermediate 1-4

(11) To a 1 L one-neck flask, was added 45 g 3,5-diphenylphenyl boronic acid and 42.5 g 1-bromo-4-iodobenzene, 450 ml dioxane, 150 ml 2M potassium carbonate aqueous solution, and 1.7 g tetrakis(triphenylphosphine)palladium under nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, concentrated, and the crude product was recrystallized from ethanol to yield 54.6 g product (95%).

(12) Synthesis of Intermediate 1-5

(13) With the protection of nitrogen, 20 g intermediate 1-4 and 300 ml THF were added into a 1 L three-necked flask. To the above solution was added dropwise 21 ml 2.5M n-butyl lithium under ?78? C. and kept for 2 hours. Then 16.6 g triisopropyl borate was added and kept for another hour. The mixture was allowed to warm to room temperature and reacted for another 12 hours. The reaction mixture was neutralized with 2N dilute hydrochloric acid, and extracted three times with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the crude product was recrystallized from ethyl acetate and n-hexane to yield 14 g product (78%).

(14) Synthesis of Intermediate 1-6

(15) To a 500 ml single-neck flask, was added 20 g intermediate 1-3, 14 g 9-anthraceneboronic acid, 350 ml dioxane, 70 ml potassium carbonate solution, and 0.6 g tetrakis(triphenylphosphine)palladium under nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and concentrated. The crude product was stirred in boiling THF, cooled down, filtered, and dried to yield 20 g product (80%).

(16) Synthesis of Intermediate 1-7

(17) To a 500 ml single-neck flask, was added 20 g intermediate 1-6, 10.4 g NBS and 400 ml chloroform. The mixture was stirred at 25? for 12 hours, then concentrated, and recrystallized from THF and ethanol to give 17 g product (73.3%).

(18) Synthesis of Compound 110

(19) To a 250 ml single-neck flask, was added 5.5 g intermediate 1-5, 7.3 g intermediate 1-7, 75 ml dioxane, 20 ml 2M potassium carbonate aqueous solution, 0.15 g tetrakis(triphenylphosphine)palladium under nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and concentrated. The crude product was stirred in boiling THF, cooled down, filtered, and dried to give 7.7 g product (75.5%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2), ?: 7.99-8.02 (m, 5H), 7.88-7.95 (m, 3H), 7.76-7.86 (m, 12H), 7.38-7.63 (m, 22H); MALDI-TOF-MS m/z found 786.5, C.sub.62H.sub.42 [M.sup.+] requires 786.3. The .sup.1H NMR of compound 110 is shown in FIG. 2.

Embodiment 2

(20) Synthesis of Compound 122

(21) ##STR00039##

(22) Synthesis of Intermediate 2-2

(23) With the protection of nitrogen, 36.3 g intermediate (2-1) and 400 ml THF were added into a 1 L three-necked flask, which was cooled down to ?78? C. followed by adding dropwise 50 ml 2.5M n-butyl lithium and kept stirring for 2 hours. Then 30 g triisopropyl borate was added and the mixture was kept stirring at low temperature for another 1 hour before allowed to warm to room temperature and stirred for another 12 hours. 2N dilute hydrochloric acid was added to neutralize the reaction mixture, which was then extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, concentrated, and recrystallized from ethyl acetate and n-hexane to yield 27 g product (90%).

(24) Synthesis of Intermediate 2-3

(25) To a 500 ml one-neck flask, was added 25 g intermediate 2-2, 14.5 g 1-bromo-4-iodobenzene, 300 ml dioxane, 60 ml 2M potassium carbonate aqueous solution, 0.6 g tetrakis(triphenylphosphine)palladium under nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and concentrated. The crude product was washed in refluxing THF, cooled down, filtered, and dried to yield 22 g product (70%).

(26) Synthesis of Intermediate 2-4

(27) With the protection of nitrogen gas, 15.5 g intermediate 2-3 and 300 ml THF was added into a 250 ml three-necked flask, which was cooled down to ?78? C. followed by adding dropwise 17 ml 2.5M n-butyl lithium and kept stirring for 2 hours. Then 10.2 g triisopropyl borate was added and the mixture was kept stirring at low temperature for another 1 hour before allowed to warm to room temperature and stirred for another 12 hours. 2N dilute hydrochloric acid was added to neutralize the reaction mixture, which was then extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, concentrated, and the crude product recrystallized from ethyl acetate and n-hexane to yield 14 g product (90%).

(28) Synthesis of Compound 122

(29) To a 250 ml single-neck flask was added 7 g intermediate 2-5, 8 g intermediate 1-7, 120 ml dioxane, 24 ml 2M potassium carbonate aqueous solution, 0.16 g tetrakis(triphenylphosphine)palladium under nitrogen. The mixture was refluxed for 12 hours, cooled down, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was washed in refluxing THF, cooled down, filtered and dried to yield 10 g product (79%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2,) ?: 7.98-8.00 (d, J=8.4 Hz, 2H), 7.94-7.96 (d, J=7.6 Hz, 2H), 7.89-7.91 (d, J=8.0 Hz, 2H), 7.76-7.86 (m, 12H), 7.65-7.67 (d, J=8.4 Hz, 2H), 7.48-7.58 (m, 11H), 7.32-7.43 (m, 11H), 7.09-7.17 (m, 6H) 2.32 (s, 3H). The calculated value of MALDI-TOF-MS m/s C.sub.70H.sub.48:888.4; measured value [M.sup.+]: 888.7.

Embodiment 3

(30) An illustrative preparation process of blue OLED adopting the organic electronic material in the present invention is given as below.

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

(32) A 5 nm-thick film of MoO.sub.3 was evaporated on top of ITO, which is used as the hole injection layer 30.

(33) A 50 nm-thick film of P1 was evaporated as the hole transport layer 40.

(34) A 20 nm-thick film of compound 110 was evaporated above the hole transport layer as the light emitting layer 50.

(35) A 40 nm-thick film of P2 was evaporated above the light emitting layer as the electron transport layer 60.

(36) Finally, a 1.2 nm-thick LiF film was evaporated as the electron injection layer 70, and a 150 nm-thick Al film was evaporated as the device cathode 80.

(37) The device could achieve blue emission with luminance of 980 cd/m.sup.2, current efficiency of 4.3 cd/A, power efficiency of 2.1 lm/W at a driving voltage of 7 V.

(38) The said structural formula of the chemicals used in the device

(39) ##STR00040##

Embodiment 4 (the Device Fabrication Procedures were the Same as that in Embodiment 3)

(40) OLED was made using compound 122 instead of compound 110.

(41) The device could achieve blue emission with luminance of 470 cd/m.sup.2, current efficiency of 4.6 cd/A, and power efficiency of 1.95 lm/W at a driving voltage of 7 V.

Comparison Example 1

(42) The device fabrication procedures were the same as that in Embodiment 3. OLED was made using the following compound P3 instead of compound 110 for comparison.

(43) The device could achieve blue emission with luminance of 289 cd/m.sup.2, current efficiency of 2.4 cd/A, and power efficiency of 1.1 lm/W at a driving voltage of 7 V.

(44) The embodiments 3 and 4 are two specific applications of the material in the present invention. The OLED devices using the invented material can achieve blue emission with higher brightness and efficiency that in the comparison example. Therefore, the stable material in the present invention is proved to give high efficiency and high color purity in electroluminescent devices.

(45) ##STR00041##