WO2019093545A1 - Phenanthroline compound and organic light emitting device comprising same - Google Patents

Abstract

The present invention relates to: a phenanthroline compound; and an organic electroluminescent device, which exhibits an excellent efficiency characteristic since one or more organic layers comprise the phenanthroline compound.

Description

Phenanthroline compounds and organic light emitting devices containing them

The present invention relates to a phenanthroline compound and an organic light emitting device comprising the same.

The organic light emitting device includes a structure in which an organic layer capable of emitting light is formed between an anode and a cathode, for converting electric energy into light energy using an organic material.

Organic light emitting devices can be formed in various structures, and a tandem type organic light emitting device in which a plurality of light emitting units are stacked has been studied.

In the tandem type organic light emitting device, a plurality of light emitting portions including a light emitting layer are stacked between the anode and the cathode. Between the adjacent light emitting portions, a charge generating layer for generating and moving charges is located.

The charge generating layer requires a low driving voltage and high efficiency.

The present invention provides a novel phenanthroline derivative which is superior in luminous efficiency and thermal stability to a conventional material, and that the phenanthroline derivative is included in the organic layer to lower the driving voltage of the device, And to provide a light emitting element.

The object of the present invention is achieved by a phenanthroline compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ is a substituted or unsubstituted aryl group having 3 to 60 carbon atoms, a substituted or unsubstituted 5 to 60 membered heteroaryl group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, an arylamine group and 2 / RTI > amine group.

The organic light emitting device includes a first electrode, a second electrode, and at least one organic layer positioned between the first electrode and the second electrode, wherein at least one of the organic layers includes the phenanthroline compound according to the present invention. .

The organic material layer may include at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes.

The organic material layer may include at least one layer selected from the group consisting of a light emitting layer, an electron injecting layer, an electron transporting layer, and layers simultaneously performing electron injection and electron transport.

The organic layer may include at least one charge generation layer (CGL).

The charge generation layer may be n-type.

Also, an object of the present invention is to provide a plasma display panel comprising a first electrode; A second electrode; And a first light emitting unit disposed between the first electrode and the second electrode and including a first light emitting layer; A second light emitting portion located between the second electrode and the first light emitting portion and including a second light emitting layer; Wherein at least one layer of the first light emitting portion, the second light emitting portion, and the first charge generating layer includes a first charge generating layer disposed between the first light emitting portion and the second light emitting portion, Can be achieved by an organic light emitting device comprising the phenanthroline compound according to claim 2.

The organic light emitting device may further include: a third light emitting portion positioned between the second electrode and the second light emitting portion and including a third light emitting layer; And a second charge generation layer disposed between the second light emitting portion and the third light emitting portion, wherein at least one layer of the third light emitting portion and the second charge generation layer is formed of the first or second light emitting portion, Lt; RTI ID = 0.0 > phenanthroline < / RTI >

The phenanthroline derivative according to the present invention may be included in an organic layer, preferably a charge generation layer, of an organic electroluminescent device, thereby lowering the driving voltage of the device and improving the luminous efficiency. Further, the lifetime of the organic electroluminescent device can be improved by the thermal stability of the phenanthroline derivative of the present invention.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

The sizes and thicknesses of the individual components shown in the figures are shown for convenience of explanation and the present invention is not necessarily limited to the size and thickness of the components shown.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The phenanthroline compound according to the present invention is represented by the formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ is a substituted or unsubstituted aryl group having 3 to 60 carbon atoms, a substituted or unsubstituted 5 to 60 membered heteroaryl group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, an arylamine group and 2 / RTI > amine group.

The compound represented by the formula (1) may be selected from the group consisting of the compounds shown below.

The phenanthroline core in the above formula (1) contains two nitrogen atoms and introduces an aromatic compound (Aromatic Compound) at the position 2 or 8 to enrich the electrons of the nitrogen atom, The electron transfer is facilitated by the mobility. In addition, nitrogen of the sp2 hybrid orbital is included in the N-type charge generation layer (N-CGL), and this nitrogen bonds with an alkali metal or an alkaline earth metal which is a dopant of the N-type charge generation layer to form a gap state . Therefore, electrons can be smoothly transferred from the P-type charge generation layer (P-CGL) to the N-type charge generation layer (N-CGL) by the gap state.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, the hole injection layer material and the hole transport layer material used in the production of an organic light emitting device have energy levels enough to transfer holes along HOMO (highest occupied molecular orbital), and the lowest unoccupied molecular orbital (LUMO) A compound capable of having an energy level enough to block the electrons passing through the electron transporting layer. Particularly, the core structure of the present compound exhibits stable characteristics in terms of electrons, which can contribute to improvement of lifetime of the device. The derivatives prepared by introducing the substituents to be used for the light emitting layer and the electron transporting layer material can be manufactured to have appropriate energy band gaps for various arylamine type dopants, aryl type dopants, metal containing dopants and the like.

 Further, by introducing various substituent groups into the core structure, it is possible to finely control the energy band gap, improve the interfacial characteristics between the organic materials, and diversify the uses of the materials.

 On the other hand, the compounds represented by Formula 1 have high glass transition temperature (Tg) and thus are excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention. Referring to FIG. 1, the organic light emitting diode 1 includes a first electrode (anode) 110, a second electrode (cathode) 120, a first light emitting portion 210, a second light emitting portion 220, A third light emitting portion 230, a first charge generating layer 240, and a second charge generating layer 250.

The first charge generating layer 240 and the second charge generating layer 250 may include a first electrode 110 as an organic material layer and a second charge generating layer 250. The first light emitting portion 210, the second light emitting portion 220, the third light emitting portion 230, The first charge generating layer 240 is located between the first light emitting portion 210 and the second light emitting portion 220 and the second charge generating layer 250 is located between the first electrode 250 and the second electrode 120, 2 light-emitting portion 220 and the third light-emitting portion 230, respectively.

The first light emitting portion 210 includes a hole injection layer 211, a first hole transporting layer 212, a first light emitting layer 213 and a first electron transporting layer 214, The second light emitting layer 222 and the second electron transporting layer 223. The third light emitting portion 230 includes the third hole transporting layer 231, the third light emitting layer 232, the third hole transporting layer 231, An electron transport layer 233, and an electron injection layer 234.

The first charge generating layer 240 is composed of an n-type charge generating layer 241 and a p-type charge generating layer 242. The second charge generating layer 250 is composed of an n-type charge generating layer 251 and a p- And a charge generation layer 252. The n-type charge generation layers 241 and 251 may be doped with an alkali metal.

The phenanthroline compound according to the present invention may be used in combination with a first electron transport layer 214, a second electron transport layer 223, a third electron transport layer 233, an electron injection layer 234, a first charge generation layer 240 and / Or the second charge generating layer 250, and can be used for the n-type charge generating layers 241 and 251 in particular.

The organic light emitting element 1 described above can be variously modified. Some organic layers may be omitted or added, may not be tandem-shaped, and may be in a tandem form having two or four or more light-emitting layers. In addition, the organic light emitting device 1 may include an organic layer including a layer simultaneously performing electron transport and electron injection, and in this case, the phenanthroline compound according to the present invention may also be used.

Hereinafter, a production example of the phenanthroline compound according to the present invention, and examples and comparative examples of the organic light emitting device will be described. However, the following Production Examples and Examples are intended only to illustrate or explain the present invention, and the present invention should not be construed to be limited by the following Production Examples and Examples.

Production Example of Compound 1-2

2- (3- (naphthalen-2-yl) -5- (phenanthrene-9-yl) phenyl) -1,10-phenanthroline represented by the above compound 1-2 was prepared using the following reactions.

Synthesis of Intermediate A (1- (3-bromo-5- (phenanthren-9-yl) phenyl) ethanone)

A round bottom flask was charged with 3,5-dibromoacetophenone (50 g, 180 mmole), phenanthrene-9-ylboronic acid (20 g, 90 mmole), tetrakis (triphenylphosphine) palladium (0) , 3%), potassium carbonate (37 g, 270 mmol), toluene (200 ml), ethanol (100 ml), and water (100 ml) were stirred under reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with hexane and the solvent was removed to give intermediate A (yield 62%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.79 (tt, 1H), 8.74 (dd, 1H), 8.18 (t, 1H), 8.05 (t, 1H), 7.92-7.89 (m, 2H) , 7.78 (dd, 1H), 7.73-7.69 (m, 2H), 7.68 (s, 1H), 7.86-7.56 (m, 2H), 2.64 (s, 3H); EI, MS m / z (%): 375 (100, M ^< ⁺ &

Synthesis of Intermediate B (1- (3- (naphthalen-2-yl) -5- (phenanthren-9-yl) phenyl) ethanone)

A round bottom flask was charged with intermediate A (11 g, 29 mmole), naphthalene-2-ylboronic acid (6 g, 35.1 mmole), tetrakis (triphenylphosphine) palladium (0) (1 g, 3% 12 g, 87.9 mmol), 110 ml of toluene, 55 ml of ethanol and 55 ml of water were added and the mixture was stirred under reflux for 6 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with methylene chloride and the solvent was removed to give Intermediate B (89% yield)

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.82 (d, 1H), 8.76 (d, 1H), 8.44 (t, 1H), 8.17 (d, 1H), 8.14 (t, 1H), 8.13 (m, 2H), 7.67-7.64 (m, 1H), 7.60-7.56 (m, (m, 1 H), 7.54-7.49 (m, 2 H), 2.74 (s, 3 H); EI, MS m / z (%): 422 (100, M ^< ⁺ &

Compound 1-2 Synthesis of 2- (3- (naphthalen-2-yl) -5- (phenanthrene-9-yl) phenyl) -1,10-phenanthroline

A round bottom flask was charged with Intermediate B (11 g, 26 mmole), 8-aminoquinoline-7-carbaldehyde (5.4 g, 31 mmole), potassium hydroxide (4.4 g, 78 mmol), toluene 110 ml, And the mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was precipitated with an excess amount of methanol, followed by filtration and drying. The column was purified with methylene chloride and the solvent was removed to obtain Compound 1-2 (yield 77%)

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.19 (dd, 1H), 8.82 (d, 1H), 8.80 (t, 1H), 8.77 (d, 1H), 8.42 (t, 1H), 8.36 (d, IH), 8.03 (t, IH), 8.00-7.88 (m, 6H) 7.82 (dd, 2H), 7.72-7.68 (m, 2H), 7.66-7.62 (m, 1H), 7.53-7.48 (m, 2H); EI, MS m / z (%): 558 (100, M ^< ⁺ &

Preparation Example of Compound 1-8

2- (3- (Phenanthren-9-yl) -5- (quinolin-3-yl) phenyl) -1,10-phenanthroline represented by the above compound 1-8 was prepared using the following reactions.

Intermediate C Synthesis of 1- (3- (phenanthren-9-yl) -5- (quinolin-3-yl) phenyl)

To a round bottom flask was added intermediate A (10 g, 26 mmole), quinoline-3-ylboronic acid (5.5 g, 31.9 mmole), tetrakis (triphenylphosphine) palladium (0) (11 g, 79.9 mmol), toluene (100 ml), ethanol (50 ml) and water (50 ml), and the mixture was refluxed for 3 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with methylene chloride and the solvent was removed to give Intermediate C (yield 88%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.28 (d, 1H), 8.82 (dd, 1H), 8.76 (dd, 1H), 8.44 (d, 1H), 8.42 (t, 1H), 8.16 (d, IH), 8.11 (t, IH), 7.97 (dd, IH), 7.91 (s, IH), 7.89 2.74 (s, 3 H); EI, MS m / z (%): 423 (100, M ^< ⁺ &

Synthesis of Compound 1-82- (3- (Phenanthrene-9-yl) -5- (quinolin-3-yl) phenyl) -1,10-phenanthroline

A round bottom flask was charged with Intermediate C (10 g, 23 mmole), 8-aminoquinoline-7-carbaldehyde (4.8 g, 28 mmole), potassium hydroxide (4 g, 71 mmol), toluene 100 ml and ethanol 50 ml And the mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was precipitated with an excess amount of methanol, followed by filtration and drying. Column purification was performed with methylene chloride, and the solvent was removed to obtain Compound 1-8 (yield 82%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ9.42 (d, 1H), 9.19 (dd, 1H), 8.83-8.76 (m, 3H), 8.57 (d, 1H), 8.44 (t, 1H 1H), 8.14 (d, 1H), 8.04 (dd, 1H), 8.01 (t, 1H), 7.97-7.91 (m, 3H), 7.82 (q, 2H), 7.76-7.69 (m, 3H), 7.67-7.63 (m, 2H), 7.57 (m, 2H); EI, MS m / z (%): 559 (100, M ^< ⁺ &

Production Example of Compound 1-10

2- (3- (Phenanthren-9-yl) -5- (pyrimidin-2-yl) phenyl) -1,10-phenanthroline represented by the above Compound 1-10 was prepared using the following reactions.

Synthesis of Intermediate D (1- (3- (phenanthren-9-yl) -5- (pyrimidin-2-yl) phenyl) ethanone)

To a round bottom flask was added intermediate A (10 g, 26 mmole), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrimidine (6.6 g, 31.9 (0.9 g, 3%), potassium carbonate (11 g, 79.9 mmol), toluene (100 ml), ethanol (50 ml) and water (50 ml) Lt; / RTI > After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was performed with methylene chloride and the solvent was removed to obtain Intermediate D (yield 62%)

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.82 (d, 1H), 8.76 (d, 1H), 8.35 (t, 1H), 8.13 (t, 1H), 8.04 (t, 1H), 7.92 (m, 2H), 7.72 (s, 1H), 7.72 (s, 1H) ); EI, MS m / z (%): 374 (100, M ^< ⁺ &

Compound 1-10 Synthesis of 2- (3- (phenanthrene-9-yl) -5- (pyrimidin-2-yl) phenyl) -1,10-phenanthroline

To a round bottom flask was added Intermediate D (6 g, 16 mmole), 8-aminoquinoline-7-carbaldehyde (3.3 g, 19 mmole), potassium hydroxide (2.7 g, 48 mmol), 60 ml of toluene and 30 ml of ethanol And the mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was precipitated with an excess amount of methanol, followed by filtration and drying. Column purification was performed with methylene chloride, and the solvent was removed to obtain Compound 1-10 (yield 91%).

Production Example of Compound 1-13

1 - (1,1'-biphenyl) -3-yl) -1, 2 '- (5- (phenanthrene- 10-phenanthroline was prepared using the following reactions.

Intermediate E Synthesis of 9- (3-bromo-5-chlorophenyl) phenanthrene

To a round bottom flask was added 1,3-dibromo-5-chlorobenzene (50 g, 184.9 mmole), phenanthrene-9-ylboronic acid (20.5 g, 92.47 mmole), tetrakis (triphenylphosphine) palladium ) (4.3 g, 4%), potassium carbonate (51 g, 369.9 mmol), toluene (500 ml), ethanol (250 ml) and water (250 ml) were added and stirred under reflux for 4 hours. After completion of the reaction, the reaction solution is filtered to obtain a crude product. The filtered crude was heated to dissolve in MC, and the column was purified on silica gel. The solvent was removed and precipitated using MC / EA to obtain Intermediate E (yield: 61%).

Intermediate F Synthesis of 2- (3'-chloro-5 '- (phenanthrene-9-yl) - [1,1'-biphenyl] -4-yl) pyrimidine

(20 g, 54.4 mmole), (4- (pyrimidin-2-yl) phenyl) boronic acid (16.1 g, 57.1 mmole), tetrakis (triphenylphosphine) palladium (0) (2.5 g, 4%), potassium carbonate (30 g, 217.6 mmol), toluene (200 ml), ethanol (100 ml), and water (100 ml) were stirred and refluxed for 6 hours. After completion of the reaction, the reaction solution is filtered to obtain a crude product. The filtered crude was heated to dissolve in MC and purified by column chromatography on silica gel. The solvent was removed and precipitated using MC / EA to give Intermediate F (81% yield).

Intermediate G 2- (3 '- (Phenanthren-9-yl) -5' - (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- , 1'-biphenyl] -4-yl) pyrimidine

To a round bottom flask was added intermediate F (10 g, 22.6 mmol), bis (pinacolato) diboron (7.5 g, 29.3 mmol), talladium acetate (253 mg, 5%), SPhos (930 mg, Potassium (14 g, 67.8 mmol) and dioxane (50 ml) were added and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the crude product is obtained by using MeOH, H ₂ O and acetone as the reaction mixture. The crude product was dissolved in MC by heating. The silica gel was purified by silica gel, and the solvent was removed. MeOH was used to obtain Intermediate G (yield: 83%). EI, MS m / z (%): 534 (100, M ^< ⁺ &

Compound 1-13 2- (5- (Phenanthren-9-yl) -4'- (pyrimidin-2-yl) - [1,1'-biphenyl] -3- Synthesis of troline

To a round bottom flask was added Intermediate G (10 g, 18.7 mmole), 2-bromo-1,10-phenanthroline (5.3 g, 57.1 mmole), tetrakis (triphenylphosphine) palladium (0) 4%), potassium carbonate (10 g, 74.8 mmol), toluene (100 ml), ethanol (50 ml) and water (50 ml) were added and stirred under reflux for 5 hours. After completion of the reaction, the reaction solution was filtered to obtain a crude product. The filtered crude was heated to dissolve in MC and purified by column chromatography on silica gel. The solvent was removed and precipitated using MC / EA to give compound 1-13 (yield: 57.4%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): 9.19 (dd, 1H), 8.84 (d, 2H), 8.77 (dd, 2H), 8.71 (t, 1H), 8.57 (tt, 2H), 8.43 ( (d, IH), 7.98-7.94 (m, 4H), 7.89 (s, IH), 7.814 (dd, 2H), 7.72-7.68 (m, 2H), 7.66-7.62 (m, 2H), 7.51 (dd, 1H), 7.2 (t, 1H); EI, MS m / z (%): 586 (100, M ^< ⁺ &

Production Example of Compound 1-16

(3- (phenanthren-9-yl) -5- (4- (pyrimidin-2-yl) naphthalen-1-yl) phenyl) -1,10-phenanthroline Was prepared using the following reactions.

Synthesis of Intermediate A (1- (3-bromo-5- (phenanthren-9-yl) phenyl) ethanone)

To a round bottom flask was added 3,5-dibromoacetophenone (50 g, 180 mmole), phenanthrene-9-ylboronic acid (20 g, 90 mmole), tetrakis (triphenylphosphine) palladium g, 3%), potassium carbonate (37 g, 270 mmol), toluene (200 ml), ethanol (100 ml), and water (100 ml) were stirred at reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with hexane and the solvent was removed to give intermediate A (yield 62%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.79 (tt, 1H), 8.74 (dd, 1H), 8.18 (t, 1H), 8.05 (t, 1H), 7.92-7.89 (m, 2H) , 7.78 (dd, 1H), 7.73-7.69 (m, 2H), 7.68 (s, 1H), 7.86-7.56 (m, 2H), 2.64 (s, 3H); EI, MS m / z (%): 375 (100, M ^< ⁺ &

Synthesis of Intermediate H Synthesis of 1- (3- (phenanthren-9-yl) -5- (4- (pyrimidin-2-yl) naphthalen-

To a round bottom flask was added intermediate A (9.5 g, 25 mmole), 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene- (10 g, 30.3 mmol), tetrakis (triphenylphosphine) palladium (0) (0.9 g, 3%), potassium carbonate (10.5 g, 75.3 mmol), toluene 100 ml, ethanol 50 ml, 50 ml of water was added and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with methylene chloride and the solvent was removed to give Intermediate H (94% yield).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.98 (s, 1H), 8.97 (s, 1H), 8.81 (d, 1H), 8.74 (d, 1H), 8.70 (d, 1H) 8.24 ( 1H), 7.81 (d, IH), 7.81 (d, IH), 7.81 (m, 2 H), 7.67-7.51 (m, 6 H), 7.34 (t, 1 H) 2.72 (s, 3 H); EI, MS m / z (%): 501 (100, M ^< ⁺ &

Compound 1-16 Synthesis of 2- (3- (phenanthren-9-yl) -5- (4- (pyrimidin-2-yl) naphthalen-1-yl) phenyl) -1,10-phenanthroline

A round bottom flask was charged with Intermediate H (14 g, 28 mmole), 8-aminoquinoline-7-carbaldehyde (5.8 g, 33.6 mmole), potassium hydroxide (4.7 g, 84 mmol), toluene 140 ml, And the mixture was refluxed for 5 hours. After completion of the reaction, the reaction mixture was precipitated with an excess amount of methanol, followed by filtration and drying. Column purification was carried out with methylene chloride and recrystallization was conducted to obtain Compound 1-16 (yield: 82%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.12 (d, 1H), 8.98 (s, 1H), 8.97 (s, 1H), 8.80 (d, 1H), 8.75 (d, 1H), 8.71 (d, 1H), 8.57 (t, 1H), 8.51 (t, 1H), 8.34 2H), 7.82 (t, 2H), 7.78 (t, 2H), 7.70-7.67 (m, 2H), 7.65-7.49 (m, 1H), 7.33 (t, 1H); EI, MS m / z (%): 637 (100, M ^< ⁺ &

Production Example of Compound 1-17

(3- (phenanthrene-9-yl) -5- (4-phenylnaphthalen-1-yl) phenyl) -1,10-phenanthroline represented by the above compound 1-17 was synthesized by the following reactions Respectively.

Synthesis of Intermediate A (1- (3-bromo-5- (phenanthren-9-yl) phenyl) ethanone)

To a round bottom flask was added 3,5-dibromoacetophenone (50 g, 180 mmole), phenanthrene-9-ylboronic acid (20 g, 90 mmole), tetrakis (triphenylphosphine) palladium g, 3%), potassium carbonate (37 g, 270 mmol), toluene (200 ml), ethanol (100 ml), and water (100 ml) were stirred at reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with hexane and the solvent was removed to give intermediate A (yield 62%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.79 (tt, 1H), 8.74 (dd, 1H), 8.18 (t, 1H), 8.05 (t, 1H), 7.92-7.89 (m, 2H) , 7.78 (dd, 1H), 7.73-7.69 (m, 2H), 7.68 (s, 1H), 7.86-7.56 (m, 2H), 2.64 (s, 3H); EI, MS m / z (%): 375 (100, M ^< ⁺ &

Intermediate I Synthesis of 1- (3- (phenanthren-9-yl) -5- (4-phenylnaphthalen-1-yl) phenyl)

To a round bottom flask was added intermediate A (15 g, 40 mmole), 2 (4-phenylnaphthalen-1-yl) boronic acid (12 g, 48 mmole), tetrakis (triphenylphosphine) palladium , 3%), potassium carbonate (16.6 g, 120 mmol), toluene (150 ml), ethanol (75 ml), and water (75 ml) were stirred under reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with methylene chloride, and the organic layer was separated and dried with MgSO ₄ . Column purification was carried out with hexane: ethyl acetate (10: 1) and the solvent was removed to give Intermediate I (92% yield).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.81 (d, 1H), 8.74 (d, 1H), 8.24 (d, 2H), 8.05 (d, 1H), 8.02-7.98 (m, 2H) 1H), 7.96-7.58 (m, 2H), 7.55-7.68 (m, 2H) 7.44 (m, 8 H), 2.72 (s, 3 H); EI, MS m / z (%): 499 (100, M ^< ⁺ &

Compound 1-17 Synthesis of 2- (3- (phenanthrene-9-yl) -5- (4-phenylnaphthalen-1-yl) phenyl) -1,10-phenanthroline

(22 g, 44 mmole), 8-aminoquinoline-7-carbaldehyde (9.2 g, 53 mmole), potassium hydroxide (7.5 g, 133 mmol), toluene 220 ml and ethanol 11 ml were added to a round bottom flask And the mixture was refluxed for 5 hours. After completion of the reaction, the reaction mixture was precipitated with an excess amount of methanol, followed by filtration and drying. Column purification was carried out with methylene chloride and recrystallization was conducted to obtain Compound 1-16 (yield 78%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 9.13 (dd, 1H), 8.80 (d, 1H), 8.75 (d, 1H), 8.56 (t, 1H), 8.52 (t, 1H) 8.34 ( 1H), 7.85 (d, 2H), 7.85 (d, 1H), 8.25 (dd, , ≪ / RTI > 2H), 7.71 (d, 1H), 7.70-7.43 (m, 13H); EI, MS m / z (%): 635 (100, M ^< ⁺ &

Manufacture of organic light emitting device

The N-CGL characteristics can be confirmed by doping the second electron transporting layer with an alkali metal such as Li in the organic light emitting device.

1. Production Example of Comparative Example

The ITO substrate was patterned to have a light emitting area of 2 mm x 2 mm, and then washed with isopropyl alcohol and UV ozone, respectively. Thereafter, the ITO substrate was mounted on a substrate holder of a vacuum deposition apparatus, and the pressure was adjusted so that the degree of vacuum was 1 x 10 < ^-7 > torr.

First, a HAT-CN compound was vacuum deposited to form a 5 nm thick layer. This compound served as a first hole injection layer, and NPB material was formed thereon as a first hole transport layer to a thickness of 35 nm.

Thereafter, the CPB material was hosted and the Ir compound was co-deposited to a thickness of 30 nm so as to have a mass ratio of about 10% with a dopant to form a yellow first light emitting layer.

A TmPyPB compound was formed on the light emitting layer to a thickness of 25 nm to form a first electron transport layer. Then, an N-type charge generation layer was formed by co-depositing a Li material to a BPhen material to a thickness of 10 nm to a mass ratio of 2%. Then, a HAT-CN compound was vacuum deposited as a P-type charge generation layer to a thickness of 5 nm. This material also serves as a second hole injection layer. On this layer, NPB material was formed to a thickness of 35 nm as a second hole transporting layer.

Then, a second yellow light emitting layer was formed by co-depositing a CPB material as a host and a 30 nm thick Ir compound as a dopant in a thickness of about 10% to form a second electron transporting layer having a thickness of 25 nm Then, a LiF material was vacuum deposited as an electron injection layer to a thickness of 1 nm. Lastly, Al was deposited to a thickness of 100 nm to form a cathode, thereby fabricating an organic EL device.

2. Production Example of Example 1

Except that only the organic material of the N-type charge generation layer was replaced with the compound 1-2 to prepare an organic light emitting device.

3. Production Example of Example 2

Except that only the organic material of the N-type charge generation layer was changed to the compound 1-13 to prepare an organic light emitting device.

4. Production Example of Example 3

Except that only the organic material of the N-type charge generation layer was replaced with the compound 1-8 to prepare an organic light emitting device.

5. Production Example of Example 4

Except that only the organic material of the N-type charge generation layer was changed to the compound 1-17 to prepare an organic light emitting device.

The current density, the driving voltage, the current efficiency, and the external quantum efficiency of the organic light emitting devices of Examples 1 to 4 and Comparative Example 1 were measured and are shown in Table 1 below.

	matter	Driving current J (mA / cm 2 )	The driving voltage	Current efficiency (cd / A)	EQE (%)
Comparative Example 1	BPhen	10	9.4	107.8	35
Example 1	1-2	10	8.78	127.4	40.7
Example 2	1-13	10	8.72	134.3	43.1
Example 3	1-8	10	8.43	123.9	40.3
Example 4	1-17	10	8.00	122.5	40.7

It can be seen that the driving voltage and the current efficiency of Examples 1 to 4 are improved as compared with Comparative Example 1.

The present invention is not necessarily limited to these embodiments, and various modifications may be made without departing from the technical idea of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (9)

1. A phenanthroline compound represented by the following formula (1)

   [Chemical Formula 1]

   

   In Formula 1,

   R ₁ is a substituted or unsubstituted aryl group having 3 to 60 carbon atoms, a substituted or unsubstituted 5 to 60 membered heteroaryl group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, an arylamine group and 2 / RTI > amine group.
2. The phenanthroline compound according to claim 1, wherein the compound represented by the formula (1) is selected from the group consisting of the following compounds:

   

   
3. The first electrode,

   A second electrode, and

   And one or more organic layers disposed between the first electrode and the second electrode,

   Wherein at least one of the organic material layers comprises the phenanthroline compound according to any one of claims 1 to 3.
4. The organic light emitting device according to claim 3, wherein the organic material layer comprises at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes.
5. The organic light emitting device according to claim 3, wherein the organic material layer includes at least one layer selected from the group consisting of a light emitting layer, an electron injecting layer, an electron transporting layer, and a layer simultaneously performing electron injection and electron transporting.
6. The organic light emitting diode according to claim 3, wherein the organic layer includes at least one charge generation layer (CGL).
7. The organic light emitting device according to claim 3, wherein the charge generating layer is n-type.
8. A first electrode;

   A second electrode; And

   A first light emitting portion located between the first electrode and the second electrode and including a first light emitting layer;

   A second light emitting portion located between the second electrode and the first light emitting portion and including a second light emitting layer;

   And a first charge generation layer disposed between the first light emitting portion and the second light emitting portion,

   Wherein at least one of the first light emitting portion, the second light emitting portion, and the first charge generating layer comprises the phenanthroline compound according to any one of Claims 1 to 4.
9. 9. The method of claim 8,

   A third light emitting portion positioned between the second electrode and the second light emitting portion and including a third light emitting layer; And

   And a second charge generation layer disposed between the second light emitting portion and the third light emitting portion,

   Wherein at least one of the third light emitting portion and the second charge generating layer comprises the phenanthroline compound according to any one of Claims 1 to 3.

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