Phenanthroline-based compound for organic electroluminescence device

Abstract

The present invention discloses a phenanthroline-based compound and an organic EL device employing the compound as phosphorescent light emitting host material of a light emitting layer and/or electron transporting layer material and/or hole blocking layer material and/or a thermally activated delayed fluorescence (TADF) material of a light emitting layer which can display good performance.

Claims

1. A phenanthroline-based compound is represented by the following formula (1): ##STR00045## wherein A is selected from the group consisting of formula (2) to formula (8): ##STR00046## L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterarylene group having 3 to 30 ring carbon atoms, m represent an integer of 0 to 4, n represents an integer of 0 to 6, p represents an integer of 0 to 7, q represents an integer of 0 to 8, r represents an integer of 0 to 10, M represents a metal atom or a non-metal atom or group; X is a divalent bridge comprising atoms or groups selected from the group consisting of O, S, C(R.sub.13)(R.sub.14), NR.sub.15 and Si(R.sub.16)(R.sub.17), Ar is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, R.sub.1 to R.sub.17 are independently selected from the group consisting of a hydrogen atom, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

2. The phenanthroline-based compound according to claim 1, wherein L is represented by the following formula (9): ##STR00047## wherein X.sub.5 to X.sub.9 independently represents a nitrogen atom or C(R.sub.s), and each R.sub.s represents a hydrogen, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

3. The phenanthroline-based compound according to claim 1, wherein M represents a metal atom selected from the group consisting of Li, Na, K and Yb.

4. The phenanthroline-based compound according to claim 1, wherein M represents a non-metal atom or group bonded with oxygen, and the non-metal atom or group is selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms.

5. The phenanthroline-based compound according to claim 1, wherein the compound is represented by one of the following formulas: ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##

6. An organic electroluminescence device comprising a pair of electrodes consisting of a cathode and an anode, and between the pairs of electrodes comprising at least a light emitting layer, one or more layers of organic thin film layers, wherein at least one of the at least a light emitting layer and the one or more organic thin film layers comprises the phenanthroline-based compound with a general formula (1) according to claim 1.

7. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer comprises the phenanthroline-based compound with a general formula (1) used as a phosphorescent host material.

8. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer comprises the phenanthroline-based compound with a general formula (1) used as a thermally activated delayed fluorescence host material.

9. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer comprises the phenanthroline-based compound with a general formula (1) used as a thermally activated delayed fluorescence dopant material.

10. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer comprises a phosphorescent dopant material.

11. The organic electroluminescent device according to claim 10, wherein the phosphorescent dopant material is an iridium complex.

12. The organic electroluminescence device according to claim 6, wherein the one or more organic thin film layers comprises the phenanthroline-based compound with a general formula (1) used as an electron transporting material.

13. The organic electroluminescence device according to claim 6, wherein the one or more organic thin film layers comprises the phenanthroline-based compound with a general formula (1) used as a hole blocking material.

14. The organic electroluminescent device according to claim 6, wherein the at least a light emitting layer comprises one of the compounds as the following formulas: ##STR00064##

15. The organic electroluminescent device according to claim 6, wherein the one or more organic thin film layers are one or more electron transporting layers or one or more hole blocking layers, and at least one of the one or more electron transporting layers and the one or more hole blocking layers comprises one of the compounds as the following formulas: ##STR00065##

16. The organic electroluminescence device according to claim 15, wherein the one or more electron transporting layer comprises lithium or 8-hydroxy-quinolinolato-lithium.

17. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer emits phosphorescent light selected from the group consisting of red, blue, green and yellow lights.

18. The organic electroluminescence device according to claim 6, wherein the at least a light emitting layer emits thermally activated delayed fluorescent light selected from the group consisting of red, blue, green and yellow lights.

19. The organic electroluminescence device according to claim 6, wherein the device is an organic light emitting device.

20. The organic electroluminescent device according to claim 6, wherein the device is a lighting panel.

21. The organic electroluminescent device according to claim 6, wherein the device is a backlight panel.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows one example of an organic EL device in the present invention, wherein 6 is transparent electrode, 14 is metal electrode, 7 is hole injection layer which is deposited onto 6, 8 is hole transporting layer which is deposited onto 7, 9 is electron blocking layer which is deposited onto 8, 10 is light emitting layer which is deposited onto 9, 11 is hole blocking layer which is deposited onto 10, 12 is electron transporting layer which is deposited on to 11, and 13 is electron injection layer which is deposited on to 12.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(2) What is probed into the invention is a phenanthroline-based compound for an organic EL device and the associated device. Detailed descriptions of the production, structure and elements will be provided in the following to make the invention thoroughly understood. Obviously, the application of the invention is not confined to specific details familiar to those who are skilled in the art. On the other hand, the common elements and procedures that are known to everyone are not described in details to avoid unnecessary limits of the invention. Some preferred embodiments of the present invention will now be described in greater detail in the following. However, it should be recognized that the present invention can be practiced in a wide range of other embodiments besides those explicitly described, that is, this invention can also be applied extensively to other embodiments, and the scope of the present invention is expressly not limited except as specified in the accompanying claims.

(3) In one embodiment of the present invention, the phenanthroline-based compound which can be used as phosphorescent light emitting host material of a light emitting layer, and/or electron transporting layer material, and/or hole blocking layer material, and/or thermally activated delayed fluorescence (TADF) material of a light emitting layer for an organic EL device is disclosed. The mentioned phenanthroline-based compound is represented by the following formula (1):

(4) ##STR00003##
wherein A is selected from the group consisting of formula (2) to formula (8)

(5) ##STR00004##
L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterarylene group having 3 to 30 ring carbon atoms, m represent an integer of 0 to 4, n represents an integer of 0 to 6, p represents an integer of 0 to 7, q represents an integer of 0 to 8, r represents an integer of 0 to 10, M represents a metal atom or a non-metal atom; X is a divalent bridge comprising atoms or groups selected from the group consisting of O, S, C(R.sub.13)(R.sub.14), NR.sub.15 and Si(R.sub.16)(R.sub.17), Ar is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, R.sub.1 to R.sub.17 are independently selected from the group consisting of a hydrogen atom, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

(6) According to the above-mentioned phenanthroline-based compound represented by formula (1), wherein L is represented by the following formula (9):

(7) ##STR00005##
wherein X.sub.5 to X.sub.9 independently represents a nitrogen atom or C(R.sub.s), and each R.sub.s represents a hydrogen, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

(8) In one embodiment, some phenanthroline-based compounds are shown below:

(9) ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021##

(10) Detailed preparation for the phenanthroline-based compound in the present invention could be clarified by exemplary embodiments, but the present invention is not limited to exemplary embodiments. EXAMPLE 1 to EXAMPLE 9 show the examples for preparation of the phenanthroline-based compound in the present invention. EXAMPLE 10 and 11 show the fabrication of an organic EL device and I-V-B, half-life time testing report of the organic EL device.

Example 1

Synthesis of C1

Synthesis of 2-(2-methoxyphenyl)-1,10-phenanthroline

(11) ##STR00022##

(12) The compound is synthesized by the method provided in Journal of Coordination Chemistry, 62(3), 400-409; 2009. A solution of n-BuLi (107.0 mmol) in hexanes was added to a solution of 2-bromoanisole (20.0 g, 107.0 mmol) in THF (80 mL) under a nitrogen atmosphere at −78° C. The mixture was allowed to warm to room temperature and stirred overnight. The resulting mixture was added dropwise to an ice-cooled solution of 1,10-phenanthroline (9.6 g, 53.5 mmol) in THF (80 mL), and a wine-red solution was obtained. The resulting mixture was refluxed for 12 h, cooled in an ice bath and quenched with water (30 mL). The organic phase was separated and stirred over MnO.sub.2 for 24 h, then filtered and dried with anhydrous MgSO.sub.4. Remove the solution to get the crude product then further purified by column chromatography on silica gel with dichloromethane as eluent. 2-(2-methoxyphenyl)-1,10-phenanthroline was obtained as a yellow oil (5.3 g, 35% yield). 1H NMR (CDCl.sub.3, 400 MHz): chemical shift (ppm) 9.27 (d, 1H), 8.35 (d, 1H), 8.22 (d, 1H), 8.17 (d, 1H), 7.87 (d, 1H), 7.82 (d, 1H), 7.69 (t, 1H), 7.43 (t, 1H), 7.15 (t, 1H), 7.03 (d, 1H), 3.89 (s, 3H).

(13) ##STR00023##

(14) A mixture of 3 g (0.01 mmol) of 2-(2-methoxyphenyl)-1,10-phenanthroline and hydrogen peroxide (0.2 mol), and acetic acid (30 ml) then heated at 80° C. for 3 h. After finishing the reaction, the mixture was allowed to cool to room temperature then poured into the ice water. The reaction mixture was extracted with dichloromethane, dried with anhydrous MgSO.sub.4, the solvent was removed and to afforded crude product (2.9 g, 96% yield), and then used in next step without purification.

(15) ##STR00024##

(16) A mixture of 2.9 g (0.01 mmol) of 9-(2-methoxyphenyl)-1,10-phenanthroline-1-oxide and 14.5 g of sodium chloride, and DMF (15 ml). 4.6 ml (0.05 mmol) of phosphoryl chloride was dropwised into then reflux 2 h. The reaction was poured into ice and filtered to get the crude. The crude was purified by column chromatography on silica to afforded product as a yellow solid (0.7 g, 22% yield). 1H NMR (CDCl.sub.3, 400 MHz): chemical shift (ppm) 8.22-8.25 (m, 3H), 8.17 (d, 1H), 7.82 (d, 1H), 7.75 (d, 1H), 7.66 (d, 1H), 7.41 (t, 1H), 7.16 (t, 1H), 7.02 (d, 1H), 3.89 (s, 3H). MS (m/z, EI.sup.+): 321.1.

(17) ##STR00025##

(18) A mixture of 2 g (6.2 mmol) of 2-chloro-9-(2-methoxyphenyl)-1,10-phenanthroline, 2.1 g (7.4 mmol) of 3-(9H-carbazol-9-yl)phenylboronic acid, 0.22 g (0.2 mmol) of Pd(PPh.sub.3).sub.4, 3.1 ml of 2M Na.sub.2CO.sub.3(aq), 10 ml of EtOH and 20 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with dichloromethane and water, dried with anhydrous MgSO.sub.4, the solvent was removed and the residue was purified by column chromatography on silica to give product (1.8 g, 55% yield) as a yellow solid. 1H NMR (CDCl.sub.3, 400 MHz): chemical shift (ppm) 8.60 (dd, 1H), 8.50 (d, 1H), 8.10-8.32 (m, 7H), 7.75˜7.81 (m, 3H), 7.64 (d, 1H), 7.51 (d, 1H), 7.3˜7.41 (m, 3H), 7.27 (t, 2H) 6.95 (dd, 2H), 3.89 (s, 3H). MS (m/z, EI.sup.+): 527.1.

(19) ##STR00026##

(20) A mixture of 1 g (1.9 mmol) of 2-(3-(9H-carbazol-9-yl)phenyl)-9-(2-methoxyphenyl)-1,10-phenanthroline and Dichloromethane (20 ml) was prepared. Phosphorus tribromide was added dropwise thereto and then the mixture was stirred for 2 h until the reaction finished. The reaction mixture was extracted with dichloromethane and water, dried with anhydrous MgSO.sub.4, the solvent was removed to give crude (0.63 g, 65%). MS (m/z, EI.sup.+): 514.2.

(21) ##STR00027##

(22) An ethanol solution (80 ml) of 2-(9-(3-(9H-carbazol-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol (1 g, 1.9 mmol) was slowly added to an ethanol solution (5 ml) of lithium hydroxide monohydrate (0.8 g, 1.50 mmol), and the mixture was stirred at room temperature. After 4 h, the solvent was in vacuum to give a yellow solid. The obtained yellow solid was purified with sublimation to give compound C1 (0.5 g, 48% yield). 1H NMR (CDCl.sub.3, 400 MHz): chemical shift (ppm) 8.60 (dd, 1H), 8.50 (d, 1H), 8.10-8.32 (m, 7H), 7.74-7.82 (m, 3H), 7.64 (d, 1H), 7.50 (d, 1H), 7.32-7.41 (m, 3H), 7.25 (t, 2H) 6.81-6.96 (dd, 2H). MS (m/z, EI.sup.+): 519.2.

Example 2

Synthesis of C5

Synthesis of 2-(9-(3-isopropyl-5-(3-isopropyl-9H-carbazol-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol, lithium salt

(23) 3-isopropyl-5-(3-isopropyl-9H-carbazol-9-yl)phenylboronic acid instead of 3-(9H-carbazol-9-yl)phenylboronic acid, except for using the same method as in synthesis Example 1, the desired compound of 2-(9-(3-isopropyl-5-(3-isopropyl-9H-carbazol-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol, lithium salt (C5) was obtained. MS (m/z, EI.sup.+): 604.6.

Example 3

Synthesis of C13

Synthesis of 2-(9-(3-(9H-3,9′-bicarbazol-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol, lithium salt

(24) 3-(9H-3,9′-bicarbazol-9-yl)phenylboronic acid instead of 3-(9H-carbazol-9-yl)phenylboronic acid, except for using the same method as in synthesis Example 1, the desired compound of 2-(9-(3-(9H-3,9′-bicarbazol-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol, lithium salt (C13) was obtained. MS (m/z, EI.sup.+): 685.3

Example 4

Synthesis of C18

Synthesis of 11-(3-(9-(2-methoxyphenyl)-1,10-phenanthrolin-2-yl)phenyl)-12-phenyl-11,12-dihydroindolo[2,3-a]carbazole

(25) ##STR00028##

(26) A mixture of 2 g (6.2 mmol) of 2-chloro-9-(2-methoxyphenyl)-1,10-phenanthroline, 3.9 g (7.4 mmol) of 11-phenyl-12-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-11,12-dihydroindolo[2,3-a]carbazole, 0.22 g (0.2 mmol) of Pd(PPh.sub.3).sub.4, 3.1 ml of 2M Na.sub.2CO.sub.3(aq), 12 ml of EtOH and 24 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the resulting mixture was allowed to cool to room temperature, then an organic layer was extracted therefrom using dichloromethane and water, and dried with anhydrous MgSO.sub.4, the solvent was removed and the residue was purified by column chromatography on silica to give product (1.8 g, 44%) as a yellow solid. MS (m/z, EI.sup.j): 693.8.

(27) ##STR00029##

(28) A mixture of 1.8 g (2.6 mmol) of 11-(3-(9-(2-methoxyphenyl)-1,10-phenanthrolin-2-yl)phenyl)-12-phenyl-11,12-dihydroindolo[2,3-a]carbazole and dichloromethane (30 ml) was prepared. Phosphorus tribromide was dropwise thereto then stirred for 2 h until the reaction finished. The reaction mixture was extracted with dichloromethane and water, dried with anhydrous MgSO.sub.4, the solvent was removed to give crude (0.91 g, 51% yield). MS (m/z, EI.sup.+): 679.1.

(29) ##STR00030##

(30) A ethanol solution (180 ml) of a 2-(9-(3-(12-phenylindolo[2,3-a]carbazol-11(12H)-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol (0.91 g, 1.3 mmol) was slowly added to a ethanol solution (5 ml) of lithium hydroxide monohydrate (0.05 g, 1.3 mmol), and the mixture was stirred at room temperature. After 4 h, the solvent was evaporated in vacuum to give a yellow solid. The obtained solid were purified with sublimation to give compound C18 (0.34 g, 38% yield). MS (m/z, EI.sup.+): 685.5.

Example 5

Synthesis of C19

Synthesis of 1-(3-(9-(2-methoxyphenyl)-1,10-phenanthrolin-2-yl)phenyl)-3,3-dimethyl-1,3-dihydroindeno[2,1-b]carbazole

(31) 3,3-dimethyl-1-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3-dihydroindeno[2,1-b]carbazole instead of 11-phenyl-12-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-11,12-dihydroindolo[2,3-a]carbazole, except for using the same method as in synthesis Example 4, the desired compound of 1-(3-(9-(2-methoxyphenyl)-1,10-phenanthrolin-2-yl)phenyl)-3,3-dimethyl-1,3-dihydroindeno[2,1-b]carbazole (C19) was obtained. MS (m/z, EI.sup.+): 644.8.

Example 6

Synthesis of C28

Synthesis of 2-(2-methoxyphenyl)-9-(4-(10-(naphthalen-1-yl) anthracen-9-yl)phenyl)-1,10-phenanthroline

(32) ##STR00031##

(33) A mixture of 2 g (6.2 mmol) of 2-chloro-9-(2-methoxyphenyl)-1,10-phenanthroline, 3.7 g (7.4 mmol) of 4,4,5,5-tetramethyl-2-(4-(10-(naphthalene-1-yl)anthracen-9-yl)phenyl)-1,3,2-dioxaborolane, 0.22 g (0.2 mmol) of Pd(PPh.sub.3).sub.4, 3.1 ml of 2M Na.sub.2CO.sub.3(aq), 10 ml of EtOH and 20 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature, then an organic layer was extracted therefrom using dichloromethane and water and dried with anhydrous MgSO.sub.4 to remove solvent to form a residue. The residue was purified by column chromatography on silica to give product (2.1 g, 53% yield) as a yellow solid. MS (m/z, EI.sup.+): 664.7.

(34) ##STR00032##

(35) A mixture of 2 g (3.0 mmol) of 2-(2-methoxyphenyl)-9-(4-(10-(naphthalen-1-yl)-anthracen-9-yl)phenyl)-1,10-phenanthroline and dichloromethane (20 ml) was prepared. Phosphorus tribromide was added dropwise thereto then the mixture was stirred 2 h until the reaction finished. The reaction mixture was extracted with dichloromethane and water, dried with anhydrous MgSO.sub.4, the solvent was removed to give crude (2.1 g, 70% yield). MS (m/z, EI.sup.+): 650.3.

(36) ##STR00033##

(37) An ethanol solution (200 ml) of 2-(9-(4-(10-(naphthalen-1-yl) anthracen-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol (1 g, 1.9 mmol) was slowly added to an ethanol solution (5 ml) of lithiumhydroxide monohydrate (0.06 g, 1.9 mmol), and the mixture was stirred at room temperature. After 4 h, the solvent was evaporated in vacuum to give a yellow solid. The obtained solid was purified with sublimation to give the compound C28 (0.56 g, 56% yield). MS (m/z, EI.sup.+): 657.7.

Example 7

Synthesis of C35

Synthesis of 2-(9-(4-(10-phenylanthracen-9-yl)naphthalen-1-yl)-1,10-phenanthrolin-2-yl)phenol, lithium salt

(38) 4,4,5,5-tetramethyl-2-(4-(10-phenylanthracen-9-yl)naphthalene-1-yl)-1,3,2-dioxaborolane instead of 4,4,5,5-tetramethyl-2-(4-(10-(naphthalene-1-yl)anthracen-9-yl)phenyl)-1,3,2-dioxaborolane, except for using the same method as in synthesis Example 6, the desired compound of 2-(9-(4-(10-phenylanthracen-9-yl)naphthalen-1-yl)-1,10-phenanthrolin-2-yl) phenol, lithium salt (C35) was obtained. MS (m/z, EI.sup.+): 655.9.

Example 8

Synthesis of C38

Synthesis of 2-(2-methoxyphenyl)-9-(4-(triphenylen-2-yl)phenyl)-1,10-phenanthroline

(39) ##STR00034##

(40) A mixture of 2 g (6.2 mmol) of 2-chloro-9-(2-methoxyphenyl)-1,10-phenanthroline, 3.6 g (7.4 mmol) of 4,4,5,5-tetramethyl-2-(4-(triphenylen-2-yl)phenyl)-1,3,2-dioxaborolane, 0.22 g (0.2 mmol) of Pd(PPh.sub.3).sub.4, 3.1 ml of 2M Na.sub.2CO.sub.3(aq), 20 ml of EtOH and 40 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature, then an organic layer was extracted therefrom using dichloromethane and water and dried with anhydrous MgSO.sub.4 to remove solvent to form a residue. The residue was purified by column chromatography on silica to give product (2.2 g, 70% yield) as a yellow solid. MS (m/z, EI.sup.+): 588.7.

(41) ##STR00035##

(42) A mixture of 2.2 g (3.0 mmol) of 2-(2-methoxyphenyl)-9-(4-(triphenylen-2-yl)phenyl)-1,10-phenanthrolineline and dichloromethane (20 ml) was prepared. Phosphorus tribromide was added dropwise thereto and then the mixture was stirred for 2 h until the reaction finished. The reaction mixture was extracted with dichloromethane and water, dried with anhydrous MgSO.sub.4, and the solvent was removed to give crude (1.5 g, 66% yield). MS (m/z, EI.sup.+): 574.7.

(43) ##STR00036##

(44) An ethanol solution (300 ml) of a 2-(9-(4-(10-(naphthalen-1-yl) anthracen-9-yl)phenyl)-1,10-phenanthrolin-2-yl)phenol (1.5 g, 2.6 mmol) was slowly added to a ethanol solution (10 ml) of lithium hydroxide monohydrate (0.1 g, 2.6 mmol), and the mixture was stirred at room temperature. After 4 h, the solvent was evaporated in vacuum to give a yellow solid. The obtained solid were purified with sublimation to give compound C38 (0.56 g, 56%). MS (m/z, EI.sup.+): 580.7.

Example 9

Synthesis of C46

Synthesis of 2-(9-(9,9-dimethyl-7-(triphenylen-2-yl)-9H-fluoren-2-yl)-1,10-phenanthrolin-2-yl)phenol, lithium salt

(45) 9,9-dimethyl-7-(triphenylen-2-yl)-9H-fluoren-2-ylboronic acid instead of 4,4,5,5-tetramethyl-2-(4-(triphenylen-2-yl)phenyl)-1,3,2-dioxaborolane, except for using the same method as in synthesis Example 8, the desired compound of 2-(9-(9,9-dimethyl-7-(triphenylen-2-yl)-9H-fluoren-2-yl)-1,10-phenanthrolin-2-yl)phenol, lithium salt (C46) was obtained. MS (m/z, EI.sup.+): 697.0

General Method of Producing Organic EL Device

(46) ITO-coated glasses with 9˜12 ohm/square in resistance and 120˜160 nm in thickness are provided (hereinafter ITO substrate) and cleaned in a number of cleaning steps in an ultrasonic bath (e.g. detergent, deionized water). Before vapor deposition of the organic layers, cleaned ITO substrates are further treated by UV and ozone. All pre-treatment processes for ITO substrate are under clean room (class 100).

(47) These organic layers are applied onto the ITO substrate in order by vapor deposition in a high-vacuum unit (10.sup.−7 Torr), such as: resistively heated quartz boats. The thickness of the respective layer and the vapor deposition rate (0.1˜0.3 nm/sec) are precisely monitored or set with the aid of a quartz-crystal monitor. It is also possible, as described above, for individual layers to consist of more than one compound, i.e. in general a host material doped with a dopant material. This is achieved by co-vaporization from two or more sources.

(48) Dipyrazino[2,3-f:2,3-]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) is used as hole injection layer material in an organic EL device, and N4,N4′-di(biphenyl-4-yl)-N4,N4′-diphenylbiphenyl-4,4′-diamine (HT1) is used as the hole transporting layer, N-(biphenyl-4-yl)-9,9-dimethyl-N-(4′-phenyl biphenyl-4-yl)-9H-fluoren-2-amine (EB2) is used as electron blocking layer material, H1 and H2 are used as phosphorescent host material for comparable examples or standard with the present invention of C1, C5, C13, C18, C19, C28, C35, C38 and C46. The chemical structures of the above-mentioned compounds are shown below:

(49) ##STR00037## ##STR00038## ##STR00039## ##STR00040##

(50) Organic iridium complexes are widely used as phosphorescent dopant for light emitting layer, for example, Ir(ppy).sub.3 can be used for phosphorescent green dopant material of a light emitting layer for an organic EL device.

(51) ##STR00041##

(52) HB3 (see the following chemical structure) is used as hole blocking material (HBM) and 2-(10,10-dimethyl-10H-indeno[2,1-b] triphenylen-12-yl)-4,6-diphenyl-1,3,5-triazine (ET2) is used as electron transporting material to co-deposit with 8-hydroxyquinolato-lithium (LiQ) in an organic EL device. The chemical structures of other prior-art OLED materials for producing standard organic EL device control or comparable material for this invention shown as below:

(53) ##STR00042##

(54) A typical organic EL device consists of low work function metals, such as Al, Mg, Ca, Li and K, as the cathode by thermal evaporation, and the low work function metals can help electrons injecting the electron transporting layer from cathode. In addition, for reducing the electron injection barrier and improving the organic EL device performance, a thin-film electron injecting layer is introduced between the cathode and the electron transporting layer. Conventional materials of electron injecting layer are metal halide or metal oxide with low work function, such as: LiF, LiQ, MgO, or Li.sub.2O. On the other hand, after the organic EL device fabrication, EL spectra and CIE coordination are measured by using a PR650 spectra scan spectrometer. Furthermore, the current/voltage, luminescence/voltage and yield/voltage characteristics are taken with a Keithley 2400 programmable voltage-current source. The above-mentioned apparatuses are operated at room temperature (about 25° C.) and under atmospheric pressure.

Example 10

(55) Using a procedure analogous to the above mentioned general method, a phosphorescent emitting organic EL device having the following device structure was produced (See FIG. 1). Device: ITO/HAT-CN (20 nm)/HT1 (110 nm)/EB2 (5 nm)/phosphorescent emitting host doped 10% Ir(ppy).sub.3 (30 nm)/HB3(10 nm)/ET2 doped 40% LiQ (35 nm)/LiQ (1 nm)/Al (160 nm). The I-V-B (at 1000 nits) and half-life time of phosphorescent emitting organic EL device testing report is shown in Table 1. The half-life time is defined that the initial luminance of 3000 cd/m.sup.2 has dropped to half.

(56) TABLE-US-00001 TABLE 1 Emitting Voltage Efficiency Half-life time host (V) (cd/A) Color (hour) H1  4.5 25 green 280 C1  4.7 12 green 150 C5  5.5 15 green 100 C13 4.8 17 green 200 C18 4.2 28 green 300 C19 4.5 26 green 350 C28 7.5 10 green 130 C35 8.5 11 green  80 C38 7.5 13 green  70 C46 8.8  9 green 100

Example 11

(57) Using a procedure analogous to the above mentioned general method, a phosphorescent emitting organic EL device having the following device structure was produced (See FIG. 1). Device: ITO/HAT-CN (20 nm)/HT1 (110 nm)/EB2 (5 nm)/H2 doped 10% Ir(ppy).sub.3 (30 nm)/hole blocking material (HBM) (10 nm)/electron transport material (ETM) (30 nm)/LiQ (1 nm)/Al (160 nm). The I-V-B (at 1000 nits) and half-life time of the phosphorescent emitting organic EL device testing report is shown in Table 1. The half-life time is defined that the initial luminance of 3000 cd/m.sup.2 has dropped to half.

(58) TABLE-US-00002 TABLE 2 Voltage Efficiency Emitting Half-life time HBM ETM (V) (cd/A) Color (hour) HB3 ET2 4.5 40 green 550 HB3 C1  4.5 45 green 520 HB3 C5  4.0 36 green 550 HB3 C13 4.8 34 green 650 HB3 C18 5.5 26 green 660 HB3 C19 5.2 35 green 560 HB3 C28 3.8 52 green 580 HB3 C35 4.1 48 green 600 HB3 C38 4.0 45 green 500 HB3 C46 3.8 35 green 460

(59) In the above preferred embodiments for a phosphorescent organic EL device testing report (see Table 1 and Table 2), we show that the phenanthroline-based compound with a general formula (1) used as phosphorescent light emitting host material of a light emitting layer, and/or electron transporting layer material, and/or hole blocking layer material, and/or a thermally activated delayed fluorescence (TADF) material of a light emitting layer for an organic EL device in accordance with the present invention can display good performance than the prior art of organic EL materials.

(60) To sum up, the present invention discloses an phenanthroline-based compound which can be used as phosphorescent light emitting host material of a light emitting layer, and/or electron transporting layer material, and/or hole blocking layer material, and/or thermally activated delayed fluorescence (TADF) material of a light emitting layer for an organic EL device. The phenanthroline-based compound is represented by the following formula (1)

(61) ##STR00043##
wherein A is selected from the group consisting of formula (2) to formula (8):

(62) ##STR00044##
L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterarylene group having 3 to 30 ring carbon atoms, m represent an integer of 0 to 4, n represents an integer of 0 to 6, p represents an integer of 0 to 7, q represents an integer of 0 to 8, r represents an integer of 0 to 10, M represents a metal atom or a non-metal atom; X is a divalent bridge comprising atoms or groups selected from the group consisting of O, S, C(R.sub.13)(R.sub.14), NR.sub.15 and Si(R.sub.16)(R.sub.17), Ar is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, R.sub.1 to R.sub.17 are independently selected from the group consisting of a hydrogen atom, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

(63) Obvious many modifications and variations are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the present invention can be practiced otherwise than as specifically described herein. Although specific embodiments have been illustrated and described herein, it is obvious to those skilled in the art that many modifications of the present invention may be made without departing from what is intended to be limited solely by the appended claims.