KR101125683B1 - Organic Light Emitting Material and Organic Light Emitting Diode Having The Same - Google Patents

Abstract

The present invention relates to a compound derivative used in an organic electroluminescent device and an organic electroluminescent device using the same. More particularly, a fluorenylcarbazole derivative compound is prepared, and the device is used as a hole transport material for an organic electroluminescent device. It is to provide an organic electroluminescent device which increases the service life of the light emitting diode and is excellent in light emission luminance and light emission efficiency.

Description

Organic electroluminescent composition and organic electroluminescent device comprising same TECHNICAL FIELD

The present invention relates to an organic electroluminescent device, and more particularly, to a fluorenylcarbazole derivative used as a light emitting material of an organic electroluminescent device, and more particularly to preparing a fluorenylcarbazole compound and It is used as a hole transport material to increase the life of the device, to provide an organic electroluminescent device excellent in light emission luminance and light emission efficiency.

Organic electroluminescent devices with various advantages such as low voltage driving, self-luminous, light weight, wide viewing angle and fast response speed are one of the most researched fields as one of the next generation flat panel displays to replace LCD.

In US Pat. No. 4,356,429, Tang et al. Disclosed a two-layered organic electroluminescent device comprising two organic layers (hole transport layer and light emitting layer) sandwiched between an anode and a cathode. That is, the hole transport layer adjacent to the anode contains a hole transport material and has a function of transferring only holes to the light emitting layer mainly in the organic electroluminescent device. Similarly, the electron transport layer adjacent to the cathode contains an electron transport material, and the organic electroluminescent device device having a two-layer structure selected to mainly transmit only electrons within the organic electroluminescent device device achieves high luminous efficiency and thus substantially organic electroluminescence. The technology of the device was improved. Therefore, in terms of luminous efficiency, a multilayer structure including a hole transport layer such as a hole injection layer and a hole transporting layer, an electron transporting layer, a hole blocking layer, and the like ( Without the multilayer system, it is impossible to expect high efficiency and high luminance.

In order to realize the organic electroluminescent device device, in addition to configuring the device in the above multilayer structure, the role of the device material, in particular, the hole transport material is very important. For long life devices, the hole transport material must be thermally and electrically stable. Because of the heat generated by the device when the voltage is applied, molecules with low thermal stability have low crystal stability, resulting in rearrangement. Finally, if localization occurs and an inhomogeneous part exists, the electric field concentrates on this part. This is because it is accepted to bring about deterioration and destruction of the device. Therefore, the organic layer is usually used in an amorphous state. Furthermore, since the organic electroluminescent device is a current injection type device, if the material used has a low glass transition temperature (Tg), the heat generated during use causes the organic electroluminescent device to deteriorate and shorten the life of the device. Let's go. In this respect, materials having a high glass transition temperature are preferred.

Representative examples of hole-transfer materials used in the past include CuPC [copper phthalocyanine], m-MTDATA [4,4 ′, 4 ”-tris ( N- 3-methylphenyl- N -phenylamino) -triphenylamine], 2-TNATA [4,4 ', 4 "-tris ( N- (naphthylene-2-yl) -N -phenylamino) -triphenylamine] of 1, TPD [ N, N' -diphenyl- N, N' -di (3-methylphenyl) -4,4'-diaminobiphenyl] and NPB [ N, N' -di (naphthalen-1-yl) -N, N' -diphenylbenzidine] Etc.

[Formula 1] [Formula 2]

However, since CuPC is a metal complex, it is widely used because it has excellent adhesion to ITO substrate and is the most stable, but it is difficult to realize total color due to absorption in the visible region, and m-MTDATA or 2-TNATA have a glass transition temperature. Since not only is low as 78 ℃ and 108 ℃ but also a lot of disadvantages in the process of mass production, this also has a problem in realizing the total color. In addition, TPD or NPB also has a fatal disadvantage of shortening the life of the device for the same reason because the glass transition temperature (Tg) as low as 60 ℃ and 96 ℃, respectively.

Recently, as a hole transport material to improve these, the Republic of Korea Patent No. 10-0846586 describes a compound according to the following formula (3), Republic of Korea Patent Publication No. 10-2009-0035729 describes a compound according to the formula (4) have. However, although these compounds are used as the hole injection layer material or the hole transport layer material, there is still a disadvantage that the luminous efficiency is not sufficient.

[Formula 3] [Formula 4]

As described above, the hole transport material used in the conventional organic electroluminescent device still contains many problems, and there is a demand for improved performance having excellent physical properties. Therefore, there is an urgent need for development of an excellent material having an improved luminous efficiency of an organic electroluminescent device and having high thermal stability and high glass transition temperature.

The present invention for solving the above problems is to provide a fluorenyl carbazole compound derivative having a high glass transition temperature, an organic electroluminescent composition comprising the same, and an organic electroluminescent device. Another object of the present invention is to provide a hole transport material for an organic electroluminescent device having excellent thermal stability and a method of manufacturing the same, which can improve the luminous efficiency of the organic electroluminescent device and increase the lifetime of the device. Still another object of the present invention is to provide an organic electroluminescent device exhibiting high luminous efficiency. Another object of the present invention is to provide an organic electroluminescent device having an extended lifetime.

First, the present invention is an organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device and comprises a fluorenylcarbazole derivative represented by the following general formula (I).

[Formula I]

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or An alkyl group, R4 and R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and D is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group Provided that both R1 and R2 do not contain fluorene groups.)

Another embodiment of the invention is an organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition described above. Here, the organic electroluminescent device includes an organic light emitting diode, an organic field-effect transistor, an organic thin film transistor, an organic laser diode, an organic solar cell, an organic light emitting electrochemical cell, or an organic integrated circuit. It is apparent to those skilled in the art that various applications such as diodes can be made.

Other embodiments are described in the detailed description and drawings below.

The fluorenylcarbazole derivatives according to the present invention have excellent thermal stability because they have a high glass transition temperature and a high pyrolysis temperature of 140 ° C. or higher, and emit light using a composition including the same as a hole transport material of an organic electroluminescent device. As a result of evaluating the characteristics, the present invention showed better emission characteristics in terms of current density, luminance, highest luminance, and luminous efficiency than those of Chemical Formulas 1 to 4.

Accordingly, when an organic electroluminescent device is manufactured using the fluorenylcarbazole derivative according to the present invention as a hole transporting material, the problem of low emission luminance and low luminous efficiency, which is the biggest disadvantage of the conventional organic electroluminescent device, is simultaneously achieved. In addition to the high glass transition temperature, the thermal stability of the organic electroluminescent device is excellent. Therefore, it is not only possible to manufacture a high-performance organic electroluminescent device, but also to achieve a high efficiency, high brightness, and a long life. It can greatly contribute to commercialization.

1 is a UV / Vis for the fluorenyl carbazole derivative of formula 12 according to an embodiment of the present invention. And fluorescence spectral graphs.
2 is a differential scanning calorimetry (DSC) curve graph of the fluorenylcarbazole derivative of Formula 12 according to an embodiment of the present invention.
Figure 3 is a UV / Vis for the fluorenyl carbazole derivative of formula 37 according to an embodiment of the present invention. And fluorescence spectral graphs.
4 is a differential scanning calorimetry (DSC) curve graph of the fluorenylcarbazole derivative of Formula 37 according to an embodiment of the present invention.
5 is a diagram showing a multilayer structure of an organic electroluminescent device manufactured using a fluorenylcarbazole derivative according to an embodiment of the present invention.

The present invention is a fluorenylcarbazole derivative represented by the following formula (I), which is useful for use as a hole transport material or an organic electroluminescent material in an organic electroluminescent device, and such fluorenylcarbazole derivatives have high glass transition temperature and excellent hole Since the organic electroluminescent device is manufactured by using it as a hole transporting material, it is possible to increase the luminous efficiency and increase the lifespan of the device.

[Formula I]

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or An alkyl group, R4 and R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and D is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group Provided that both R1 and R2 do not contain fluorene groups.)

In the above formula (I), the substituted or unsubstituted aryl group means an aryl group which is substituted by a specific functional group or is not substituted by any functional group, and examples of such an aryl group are phenyl group, naphthyl group, phenanthryl group and anthryl Groups, biphenyl groups, terphenyl groups, fluorene groups and the like.

Accordingly, specific examples of the fluorenylcarbazole derivative having the structure of Formula (I), which enables the organic electroluminescent device having a particularly high luminous efficiency and long life, include a compound selected from the following Chemical Formulas 11 to 62. However, the present invention is not limited to these.

[Formula 11] [Formula 12]

[Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

[Formula 31] [Formula 32]

[Formula 33] [Formula 34]

[Formula 35] [Formula 36]

[Formula 37] [Formula 38]

[Formula 39] [Formula 40]

[Formula 41] [Formula 42]

[Formula 43] [Formula 44]

[Formula 45] [Formula 46]

[Formula 47] [Formula 48]

[Formula 49] [Formula 50]

[Formula 51] [Formula 52]

[Formula 53] [Formula 54]

[Formula 55] [Formula 56]

[Formula 57] [Formula 58]

[Formula 59] [Formula 60]

[Formula 61] [Formula 62]

The present invention may be an organic light emitting composition or an organic light emitting material or a fluorenylcarbazole derivative which may be used as a light emitting material of an organic electroluminescent device as described above. The use of such derivatives, compositions, or materials as hole transporting materials for organic electroluminescent devices yields high luminous efficiency, and because of the high glass transition temperature of the fluorenylcarbazole derivatives, devices with excellent durability can be fabricated. Here, the hole transport material refers to a material used for the hole injection layer or the hole transport layer, in some cases may be a material used for the light emitting layer.

In addition, the fluorenylcarbazole derivatives according to the present invention may be purified using recrystallization and sublimation methods due to the characteristics of the organic electroluminescent device requiring high purity.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The invention can be better understood by the following examples and comparative examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1 Preparation of Chemical Formula 11

In the present invention, the fluorenylcarbazole derivative represented by Chemical Formula I may be prepared by a synthetic route as in Scheme 1 below.

[Reaction Scheme 1]

1-1. Preparation of Chemical Formula 103

200 g (1.196 mol) of carbazole (101), 343 g of 2-bromo-9,9-dimethyl-9 H -fluorene (102) in a 3000-mL, four-necked round bottom flask under nitrogen atmosphere 1.3 g of acetate (II), 1.8 g of tri- (t-butyl) phosphine (50% hexane solution), 150 g of sodium t-butoxide and 2000 mL of O-xylene were added. The reaction solution was refluxed for 8 hours, cooled to room temperature and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 340 g (yield 79%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.25 (d, J = 8.0 Hz, 2H), 8.09 (d, J = 7.6 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.84 (s, 1H), 7.60-7.56 (m, 2H), 7.47-7.34 (m, 6H), 7.31-7.27 (m, 2H), 1.53 (s, 6H).

1-2. Preparation of Formula 104

200 g (0.556 mol) of the compound of formula 103 prepared in Example 1-1 were added to a 10000-mL, 5-neck round bottom flask and diluted with 4000 mL of chloroform. The diluent was cooled to 0 ° C., and then 99 g of N -bromosuccinimide (NBS) was slowly added thereto and stirred for 3 hours. 4000 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried, concentrated and then recrystallized with acetone and methanol and dried in vacuo to give 183 g (yield 75%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.52 (s, 1H), 8.32 (d, J = 8.0 Hz, 1H), 8.10 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.86 (s, 1H), 7.62-7.54 (m, 3H), 7.50-7.35 (m, 6H), 1.53 (s, 6H).

1-3. Preparation of Formula 105

150 g (0.342 mol) of the compound of Formula 104 prepared in Example 1-2 were added to a 5000-mL, 5-neck round bottom flask and diluted with 3500 mL of tetrahydrofuran. 50 g of benzeneboronic acid, 342 mL of 3M-potassium carbonate aqueous solution and 5.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 137 g (yield 92%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.45 (s, 1H), 8.24 (d, J = 7.6 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.79 (d, J = 7.2 Hz, 1H), 7.75 (s, 1H), 7.70-7.61 (m, 3H), 7.50-7.46 (m, 3H), 7.42-7.30 (m, 5H), 7.29-7.16 (m, 3H), 1.53 (s, 6 H).

1-4. Preparation of Formula 106

Into a 10000-mL, five-necked round bottom flask, 128 g (0.294 mol) of the Formula 105 compound prepared in Example 1-3 were added and diluted with 2500 mL of chloroform. After cooling the dilution solution to 0 ° C., 53 g of N -bromosuccinimide (NBS) was slowly added thereto, followed by stirring for 6 hours. 2500 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried, concentrated and then recrystallized with acetone and methanol and dried in vacuo to give 129 g (yield 85%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.69 (s, 1H), 8.63 (s, 1H), 8.10 (d, J = 7.6 Hz, 1H), 7.93 (d, J = 6.4 Hz, 1H ), 7.88 (s, 1H), 7.81-7.78 (m, 3H), 7.59 (s, 3H), 7.48-7.46 (m, 3H), 7.39-7.35 (m, 4H), 1.53 (s, 6H).

1-5. Preparation of Formula 107

100 g (0.194 mol) of the formula 106 compound prepared in Example 1-4 were added to a 3000-mL, four-necked round bottom flask, and diluted with 2000 mL of tetrahydrofuran. 35 g of 4-chlorobenzeneboronic acid, 194 mL of 3M-potassium carbonate aqueous solution, and 5 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 89 g (yield 84%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): 8.76 (d, J = 11.6 Hz, 2H), 8.11 (d, J = 8 Hz, 1H), 7.94-7.90 (m, 2H), 7.85-7.78 ( m, 6H), 7.61-7.42 (m, 7H), 7.38-7.35 (m, 4H), 1.55 (s, 6H).

1-6. Preparation of Formula 11

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere, 13.6 g of diphenylamine, 0.08 g of palladium acetate (II), tri- (t- 0.3 g of butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 45 g (yield 91%) of the title compound. MS ( m / z , [M] ⁺ ): C51H38N2: 678.47

Example 2 Preparation of Chemical Formula 12

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere, 17.7 g of N -phenyl-1-naphthylamine, 0.08 g of palladium acetate (II) 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 42 g (yield 79%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.67 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8 Hz, 2H), 7.94-7.77 (m, 7H), 7.73-7.69 (m, 3H), 7.63-7.57 (m, 3H), 7.54-7.32 (m, 10H), 7.25 (t, J = 7.2 Hz, 2H), 7.04- 6.94 (m, 5 H), 1.53 (s, 6 H).

UV (λ _max ): 328 nm PL: 445 nm (see Fig. 1)

Glass transition temperature (measured by Tg, DSC): 148 ℃ (see Figure 2)

Example 3 Preparation of Chemical Formula 13

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5, 17.7 g of N -phenyl-2-naphthylamine, 0.08 g of palladium acetate (II) in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 46 g (yield 87%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.72 (s, 2H), 8.11 (d, J = 8.0 Hz, 1H), 7.94-7.91 (m, 2H), 7.86-7.76 (m, 8H) , 7.71 (d, J = 8.0 Hz, 1H), 7.64-7.59 (m, 2H), 7.51-7.25 (m, 12H), 7.17-7.06 (m, 6H), 1.54 (s, 6H).

UV (λ _max ): 330 nm PL: 424 nm

Glass transition temperature (measured by Tg, DSC): 144 ℃

Example 4 Preparation of Chemical Formula 21

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere, 21.7 g of di (2-naphthyl) amine, 0.08 g of palladium acetate (II), 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 46 g (yield 81%) of the title compound. MS ( m / z , [M] ⁺ ): C59H42N2: 778.46

Example 5 Preparation of Chemical Formula 22

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5, 23.8 g of N- (4-biphenyl) -2-naphthylamine, palladium acetate, prepared in Example 1-5 in a 1000-mL, four-neck round bottom flask. (II) 0.08 g, tri- (t-butyl) phosphine (50% hexane solution) 0.3 g, sodium t-butoxide 9 g and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 45 g (yield 76%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.73 (s, 2H), 8.08 (d, J = 8 Hz, 1H), 7.92-7.71 (m, 11H), 7.63-7.56 (m, 6H) , 7.52-7.27 (m, 14H), 7.15 (dd, J = 13.6, 8.4 Hz, 4H), 1.53 (s, 6H).

UV (λ _max ): 339 nm PL: 428 nm

Glass transition temperature (measured by Tg, DSC): 158 ℃

Example 6 Preparation of Chemical Formula 25

40 g (0.073 mol) of Formula 107 compound prepared in Example 1-5, 25.9 g of di (4-biphenyl) amine, 0.08 g of palladium acetate (II), in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 43 g (yield 71%) of the title compound. MS ( m / z , [M] ⁺ ): C63H46N2: 830.46

Example 7 Preparation of Chemical Formula 28

7-1. Preparation of Formula 108

150 g (0.342 mol) of the compound of Formula 104 prepared in Example 1-2 were added to a 5000-mL, 5-neck round bottom flask and diluted with 3500 mL of tetrahydrofuran. 68 g of 1-naphthalene boronic acid, 342 mL of 3M-potassium carbonate aqueous solution and 5.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 135 g (yield 81%) of the title compound.

7-2. Preparation of Formula 109

Into a 10000-mL, 5-neck round bottom flask, 130 g (0.268 mol) of the compound of Formula 108 prepared in Example 7-1 were added and diluted with 2600 mL of chloroform. The diluent was cooled to 0 ° C., and then 50 g of N -bromosuccinimide (NBS) was slowly added thereto and stirred for 6 hours. 2600 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried, concentrated and then recrystallized with acetone and methanol and dried in vacuo to give 133 g (yield 88%) of the title compound.

7-3. Preparation of Formula 110

110 g (0.194 mol) of Chemical Formula 109 prepared in Example 7-2 were added to a 3000-mL, four-necked round bottom flask, and diluted with 2200 mL of tetrahydrofuran. 35 g of 4-chlorobenzeneboronic acid, 194 mL of 3M-potassium carbonate aqueous solution, and 5 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 88 g (yield 76%) of the title compound.

7-4. Preparation of Formula 28

43.5 g (0.073 mol) of Formula 110 compound prepared in Example 7-3, 17.7 g of N -phenyl-2-naphthylamine, 0.08 g of palladium acetate (II) in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 48 g (yield 84%) of the title compound. MS ( m / z , [M] ⁺ ): C59H42N2: 778.45

Example 8 Preparation of Chemical Formula 34

43.5 g (0.073 mol) of Formula 110 compound prepared in Example 7-3, 23.8 g of N- (4-biphenyl) -2-naphthylamine, palladium acetate, prepared in Example 7-3 in a 1000-mL, four-neck round bottom flask; (II) 0.08 g, tri- (t-butyl) phosphine (50% hexane solution) 0.3 g, sodium t-butoxide 9 g and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 49 g (yield 79%) of the title compound. MS ( m / z , [M] ⁺ ): C65H46N2: 854.48

Example 9 Preparation of Chemical Formula 36

9-1. Preparation of Formula 111

150 g (0.342 mol) of the compound of Formula 104 prepared in Example 1-2 were added to a 5000-mL, 5-neck round bottom flask and diluted with 3500 mL of tetrahydrofuran. 68 g of 1-naphthalene boronic acid, 342 mL of 3M-potassium carbonate aqueous solution and 5.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 143 g (yield 81%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.77 (s, 1H), 8.41 (d, J = 7.6 Hz, 1H), 8.34 (s, 1H), 8.12 (d, J = 8 Hz, 1H ), 7.95-7.89 (m, 7H), 7.64-7.32 (m, 10H), 1.53 (s, 6H).

9-2. Preparation of Formula 112

Into a 10000-mL, 5-necked round bottom flask, 130 g (0.268 mol) of Formula 111 compound prepared in Example 9-1 were added and diluted with 2600 mL of chloroform. The diluent was cooled to 0 ° C., and then 50 g of N -bromosuccinimide (NBS) was slowly added thereto and stirred for 6 hours. 2600 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried, concentrated and then recrystallized with acetone and methanol and dried in vacuo to give 135 g (yield 89%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.87 (s, 1H), 8.68 (s, 1H), 8.34 (s, 1H), 8.13 (d, J = 7.6 Hz, 1H), 8.06-7.90 (m, 6H), 7.64-7.49 (m, 7H), 7.43-7.34 (m, 3H), 1.53 (s, 6H).

9-3. Preparation of Formula 113

110 g (0.194 mol) of the Formula 112 compound prepared in Example 9-2 were added to a 3000-mL, four-necked round bottom flask and diluted with 2200 mL of tetrahydrofuran. 35 g of 4-chlorobenzeneboronic acid, 194 mL of 3M-potassium carbonate aqueous solution, and 5 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 94 g (yield 81%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.91 (s, 1H), 8.81 (s, 1H), 8.34 (s, 1H), 8.12 (d, J = 7.6 Hz, 1H), 8.03-7.92 (m, 7H), 7.85 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.4 Hz, 1H), 7.65-7.42 (m, 8H), 7.40-7.35 (m, 2H), 1.53 ( s, 6H).

9-4. Preparation of Formula 36

43.5 g (0.073 mol) of Formula 113 compound prepared in Example 9-3, 17.7 g of N -phenyl-1-naphthylamine, 0.08 g of palladium acetate (II) in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 46 g (yield 81%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.89 (s, 1H), 8.72 (s, 1H), 8.36 (s, 1H), 8.14 (d, J = 8.1 Hz, 1H), 8.05-7.91 (m, 10H), 7.77-7.37 (m, 15H), 7.28 (d, J = 7.3 Hz, 2H), 7.07-6.96 (m, 5H), 1.56 (s, 6H).

UV (λ _max ): 330 nm PL: 445 nm

Example 10 Preparation of Chemical Formula 37

43.5 g (0.073 mol) of Formula 113 compound prepared in Example 9-3, 17.7 g of N -phenyl-2-naphthylamine, 0.08 g of palladium acetate (II) in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 42 g (yield 74%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.90 (s, 1H), 8.76 (s, 1H), 8.35 (s, 1H), 8.12 (d, J = 7.6 Hz, 1H), 8.03-7.93 (m, 7H), 7.86-7.76 (m, 5H), 7.71 (d, J = 7.6 Hz, 1H), 7.65-7.46 (m, 7H), 7.43-7.32 (m, 6H), 7.27 (dd, J = 13.0, 7.8 Hz, 1H), 7.18-7.07 (m, 5H), 1.53 (s, 6H).

UV (λ _max ): 332 nm PL: 424 nm (see FIG. 3)

Glass transition temperature (measured by Tg, DSC): 147 ℃ (see Figure 4)

Example 11 Preparation of Chemical Formula 42

43.5 g (0.073 mol) of Formula 113 compound prepared in Example 9-3, 23.8 g of N- (4-biphenyl) -2-naphthylamine, palladium acetate, prepared in Example 9-3 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere (II) 0.08 g, tri- (t-butyl) phosphine (50% hexane solution) 0.3 g, sodium t-butoxide 9 g and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 44 g (yield 71%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.53 (s, 1H), 8.45 (s, 1H), 8.16 (s, 1H), 7.96-7.86 (m, 4H), 7.83-7.75 (m, 4H) , 7.71-7.46 (m, 18H), 7.44-7.32 (m, 7H), 7.30-7.24 (m, 4H), 1.54 (s, 6H).

UV (λ _max ): 338 nm PL: 425 nm

Example 12 Preparation of Chemical Formula 47

43.5 g (0.073 mol) of Formula 113 compound prepared in Example 9-3, 25.8 g of di (4-biphenyl) amine, 0.08 g of palladium acetate (II), in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 44 g (yield 68%) of the title compound.

¹ H NMR (400 MHz, DMSO- d ₆ ): δ 8.88 (s, 1H), 8.68 (s, 1H), 8.34 (s, 1H), 8.14 (d, J = 8.0 Hz, 1H), 8.03-7.92 (m, 7H), 7.79-7.71 (m, 4H), 7.66-7.35 (m, 18H), 7.29-7.15 (m, 5H), 6.99 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 8 Hz, 2H), 1.55 (s, 6H).

UV (λ _max ): 344 nm PL: 431 nm

Example 13 Preparation of Chemical Formula 52

13-1. Preparation of Formula 114

110 g (0.194 mol) of the Formula 112 compound prepared in Example 9-2 were added to a 3000-mL, four-necked round bottom flask and diluted with 2200 mL of tetrahydrofuran. 48 g of 4-chloronaphthalene boronic acid, 194 mL of 3M-potassium carbonate aqueous solution, and 5 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 78 g (yield 62%) of the title compound.

13-2. Preparation of Formula 52

47 g (0.073 mol) of Formula 114 compound prepared in Example 13-1, 17.7 g of N -phenyl-1-naphthylamine, 0.08 g of palladium acetate (II) in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 39 g (yield 65%) of the title compound. MS ( m / z , [M] ⁺ ): C63H44N2: 828.51

Example 14 Preparation of Chemical Formula 58

14-1. Preparation of Formula 116

100 g (0.284 mol) of the Formula 115 compound were added to a 5000-mL, 5-neck round bottom flask, and diluted with 2000 mL of tetrahydrofuran. 35 g of benzeneboronic acid, 284 mL of 3M-potassium carbonate aqueous solution and 4 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The resulting solid compound was purified by silica gel column chromatography to obtain 52 g (yield 52%) of the title compound.

14-2. Preparation of Formula 117

As shown in the figure, a compound similar to Formula 104 was prepared by the method according to Example 1 using Formula 116 prepared according to Example 14-1 instead of Compound 102 in Scheme 1 of Example 1 Using this, a compound of formula 117 similar to formula 113 was prepared by the method according to Example 9.

14-3. Preparation of Formula 58

49 g (0.073 mol) of Formula 117 compound prepared in Example 14-2 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere, 17.7 g of N -phenyl-2-naphthylamine, 0.08 g of palladium acetate (II) 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 37 g (yield 60%) of the title compound. MS ( m / z , [M] ⁺ ): C65H46N2: 854.49

Example 15 Preparation of Chemical Formula 61

15-1. Preparation of Formula 119

As shown in the figure, Compound 119 was prepared by the same method as preparing Compound 107 in Example 1, except that Compound 118 was used instead of Compound 102 in Scheme 1 of Example 1.

15-2. Preparation of Formula 61

49 g (0.073 mol) of Formula 119 compound prepared in Example 15-1 in a 1000-mL, four-necked round bottom flask under nitrogen atmosphere, 17.7 g of N -phenyl-1-naphthylamine, 0.08 g of palladium acetate (II) 0.3 g of tri- (t-butyl) phosphine (50% hexane solution), 9 g of sodium t-butoxide and 400 mL of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 32 g (yield 52%) of the title compound. MS ( m / z , [M] ⁺ ): C65H44N2: 852.47

Example 16

Fabrication of Organic Electroluminescent Device Using Formula 11

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 kPa was formed on a glass substrate having a size of 25 mm × 75 mm × 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. Subsequently, 2-TNATA of Chemical Formula 1 was deposited to have a thickness of 600 GPa to form a hole injection layer. Subsequently, the formula 11 of the present invention was deposited to a thickness of 600 kPa to form a hole transport layer. Subsequently, the light emitting layer was formed by simultaneously depositing a-ADN of Formula 5, which is a blue host, and perylene of Formula 6, which is a blue dopant, in a weight ratio of 95: 5. Subsequently, Alq ₃ of Chemical Formula 7 was deposited to have a thickness of 200 GPa to form an electron transport layer. Subsequently, lithium fluoride (LiF) was deposited to have a thickness of 10 GPa to form an electron injection layer. Finally, aluminum was deposited to have a thickness of 1000 GPa to form a cathode. The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Formula 1] [Formula 5]

[Formula 6] [Formula 7]

[Examples 17 to 30]

Fabrication of organic electroluminescent device using fluorenylcarbazole derivatives according to the present invention

In Example 16, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 16, except that the fluorenylcarbazole derivatives shown in Table 1 were used as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Comparative Examples 1 to 3]

Fabrication of Organic Electroluminescent Device Using Comparative Compound

In Example 16, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 16, except for using the following Chemical Formulas 2 to 4 shown in Table 1 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Formula 2] [Formula 3]

[Formula 4]

Luminescence Characteristics of Organic Electroluminescent Devices Example Compound of hole transport layer Brightness
(cd / m ² ) Efficiency
(cd / A) Luminous color Example 16 Formula 11 12520 4.30 blue Example 17 Formula 12 14050 7.41 blue Example 18 Formula 13 9725 6.56 blue Example 19 Formula 21 20050 6.70 blue Example 20 Formula 22 15810 7.16 blue Example 21 Formula 25 10870 7.14 blue Example 22 Formula 28 10022 4.95 blue Example 23 Formula 34 17628 7.52 blue Example 24 Formula 36 23516 6.03 blue Example 25 Formula 37 18210 4.75 blue Example 26 Formula 42 14682 6.11 blue Example 27 Formula 47 21854 5.84 blue Example 28 Formula 52 9954 3.74 blue Example 29 Formula 58 18256 4.77 blue Example 30 Formula 61 16002 4.55 blue Comparative Example 1 Formula 2 7546 3.22 blue Comparative Example 2 Formula 3 9654 3.71 blue Comparative Example 3 Formula 4 8561 3.48 blue

As can be seen in Table 1, it can be seen that the organic electroluminescent device according to Examples 16 to 30 of the present invention has a significantly higher brightness and efficiency than Comparative Examples 1 to 3 as a whole.

Simple modifications or changes of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be included in the scope of the present invention.

The organic light emitting composition and the organic electroluminescent device including the same according to the present invention are not only organic light emitting diodes but also organic field-effect transistors, organic thin film transistors, organic laser diodes, organic solar cells, organic light emitting electrochemical cells, and organic integrated circuits. Can also be used in the field.

Claims (3)

An organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device and comprises a fluorenylcarbazole derivative represented by the following general formula (I).
(I)

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or An alkyl group, R4 and R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and D is a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group Provided that both R1 and R2 do not contain fluorene groups.)
The organic electroluminescent composition according to claim 1, wherein Chemical Formula I is selected from the group consisting of Chemical Formula 11 to Chemical Formula 62.
[Formula 11] [Formula 12]

[Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

[Formula 31] [Formula 32]

[Formula 33] [Formula 34]

[Formula 35] [Formula 36]

[Formula 37] [Formula 38]

[Formula 39] [Formula 40]

[Formula 41] [Formula 42]

[Formula 43] [Formula 44]

[Formula 45] [Formula 46]

[Formula 47] [Formula 48]

[Formula 49] [Formula 50]

[Formula 51] [Formula 52]

[Formula 53] [Formula 54]

[Formula 55] [Formula 56]

[Formula 57] [Formula 58]

[Formula 59] [Formula 60]

[Formula 61] [Formula 62]

An organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition according to claim 1.

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