TWI477582B - Host emitter material and oled containing the same - Google Patents

Description

Main illuminant material and organic light emitting diode containing main illuminant material

This invention relates to a primary illuminant material, and more particularly to a phosphorescent primary illuminant material.

An organic light-emitting diode (OLED) belongs to a hole and a dual-injection element, in which a hole and an electron are injected and transmitted from an anode and a cathode to a light-emitting layer, respectively. The layers recombine and produce excitable luminescence. In order to improve luminous efficiency, the above-mentioned light-emitting region must be isolated from the electrode surface to avoid quenching of excitons. To this end, a polymer light-emitting device having a multilayer structure has been developed, and its structure is sequentially an anode, a hole-transport layer (HTL), a light-emitting layer (EL), and an electron transport layer ( Electron-transport layer) and cathode.

A primary illuminant material of a conventional organic light-emitting diode (OLED), such as 4,4',4"-tris(9-carbazolyl)triphenylamine (TcTa) or 1,3-bis(9H-carbazole- 9-yl) benzene (mcp) belongs to the main illuminant material with better hole transporting ability. However, the main illuminant material with better hole transporting ability is often insufficient due to the excited triplet state (T ₁ ). The external quantum efficiency (EQE) is lowered, resulting in poor luminous efficiency.

Therefore, an aspect of the present invention provides a main illuminant material of an organic light emitting diode (OLED). The above primary illuminant material is a carbazole derivative having the structure of the following chemical formula (I):

Wherein R ₁ and R ₂ may each independently be R ₄ or X is a sulfur linkage (-S-), a sulfoxide linkage (-SO-) or a sulfone linkage (-SO ₂ -), Y is carbon or nitrogen, and R ₄ is hydrogen. Fluorine, chlorine, bromine, iodine, C1-C30 alkyl, C1-C30 alkanol or aryl substituent, n is an integer from 0 to 2, and

For hydrogen or , R ₆ is R ₄ or , R ₄ and n are the same as described above.

According to an embodiment of the invention, wherein R ₁ of the formula (I) is hydrogen or When n = 0, X is an arylene bond (-SO-) or a hydrazone bond (-SO ₂ -), and R ₄ is hydrogen or chlorine, when R ₂ of the formula (I) is When n = 0, X is an arylene bond (-SO-) or a hydrazone bond (-SO ₂ -), R ₄ is hydrogen or chlorine, and when R ₃ of the formula (I) is When n=0, R ₄ and R ₅ are hydrogen, the structure of the above-mentioned main illuminant material is one of the following chemical structural formulas:

According to another embodiment of the present invention, wherein R ₁ and R ₂ of the formula (I) are When n = 0, R ₄ is hydrogen, X is a hydrazone bond (-SO ₂ -), Y is carbon, and when R ₃ of the formula (I) is When the structure of the main illuminant material is the following chemical structural formula:

According to another embodiment of the present invention, wherein R ₁ and R ₂ of the formula (I) are When n=0, Y is carbon, and when R ₃ of the formula (I) is When n=0, R ₅ is When R ₆ is R ₄ , the structure of the above main illuminant material is the following chemical formula (II):

According to still another embodiment of the present invention, wherein R ₁ and R ₂ of the formula (I) are When n = 0, Y is carbon, and when R ₃ of the formula (I) is When n=0, R ₅ is And R ₆ is The structure of the main illuminant material is the following chemical formula (III):

(III)

According to an embodiment of the invention, wherein R ₁ and R ₂ of the formula (I) are When Y is carbon, and when R ₃ of the formula (I) is When n is an integer from 0 to 2, the structure of the above-mentioned main illuminant material is the following chemical formula (IV):

According to an embodiment of the invention, wherein when R ₁ and R ₂ of the formula (I) are R ₄ , and when R ₃ of the formula (I) is The structure of the above main illuminant material is the following chemical formula (V):

According to another embodiment of the present invention, wherein when R ₄ of the formula (V) is hydrogen, the structure of the main illuminant material is the following chemical structural formula:

According to still another embodiment of the present invention, the excitation triplet state (T ₁ ) of the primary illuminant material is greater than 2.8 electron volts (eV).

Another aspect of the present invention provides an organic light emitting diode (OLED). The structure includes a first electrode and a second electrode opposite to the first electrode, a hole transport layer disposed between the first electrode and the second electrode, and an electron transport layer opposite to the hole transport layer, and configured to be electrically a light-emitting layer between the hole transport layer and the electron transport layer, wherein the light-emitting layer comprises a main light-emitting material and a guest light-emitting material, wherein the main light-emitting material is as described in any one of the chemical formulas (I) to (V).

According to an embodiment of the invention, the first electrode and the second electrode of the organic light emitting diode are respectively selected from one of a transparent electrode or a reflective electrode. The transparent electrode may be, for example, indium tin oxide (ITO), and the reflective electrode may be, for example, aluminum-lithium fluoride (Al/LiF).

According to another embodiment of the present invention, the hole transport layer of the organic light emitting diode is a hole transport material, and may be, for example, 4,4',4"-tris(9-carbazolyl)triphenylamine (TcTa). .

According to still another embodiment of the present invention, the cushion transfer layer of the organic light-emitting diode is an electron transport material, and may be, for example, tris(8-hydroxyquinoline)aluminum (Alq ₃ ) or 4,7-diphenyl-1. , 10-phenanthroline (Bphen).

According to still another embodiment of the present invention, the guest illuminant of the organic light-emitting diode is bis(3,5-difluorophenylpyridyl)-(2-carboxypyridyl)iridium(III) (FIrpic), double (3,5-Difluorophenylpyridinyl) tetrakis(1-pyrazolyl)borate ruthenium (III) (FIr6), bis(3,5-difluorophenylpyridinyl)-5-(2-pyridyl -1 hydrogen-tetrazolium (III) (FIrN4), bis(3,5-difluorophenylpyridyl)-3-(trifluoromethyl)-5-(2-pyridyl)-1,2 , 4-triazolium (III) (FIrtaz), tris(2-phenylpyridyl)ruthenium (III) (Irppy3), bis(2-phenylquinolinyl) (acetamidineacetone) ruthenium (III) ( PQIr), or tris(1-phenylisoquinolinyl)iridium (III) (Irpiq).

According to an embodiment of the present invention, the weight concentration percentage of the main illuminant material and the guest illuminant material is 4 times or more, and the weight concentration percentage of the guest illuminant material is not 0.

According to another embodiment of the present invention, the external quantum efficiency (EQE) of the main light-emitting layer of the organic light-emitting diode is 13 or more.

The spirit of the present invention will be clearly described in the following description and detailed description of the present invention. However, the present invention may be modified and modified by the techniques of the present invention after the embodiments of the present invention are disclosed. The spirit and scope of the invention are not departed.

Main illuminant material

One aspect of the present invention provides a main light-emitting material of an organic light-emitting diode, which is a carbazole derivative, and a method for producing the same. The structure of the above carbazole derivative is as shown in the following chemical formula (I):

Wherein R ₁ and R ₂ may each independently be R ₄ or X is a sulfur linkage (-S-), a sulfoxide linkage (-SO-) or a sulfone linkage (-SO ₂ -), Y is carbon or nitrogen, and R ₄ is hydrogen. Fluorine, chlorine, bromine, iodine, C1-C30 alkyl, C1-C30 alkanol or aryl substituent, n is an integer from 0 to 2, and

For hydrogen or , R ₆ is R ₄ or , R ₄ and n are the same as described above.

Example 1: Carbazole derivative Cbz1

Here, a carbazole derivative Cbz1 and a method for producing the same are provided, and the carbazole derivative Cbz1 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbz1 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbz1 comprises an N-phenylation reaction of carbazole, a monohalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbz1 was obtained by the above reaction process.

First process

In the N-phenylation reaction (see the first scheme), the carbazole and iodobenzene are subjected to a two-molecule nucleophilic substitution reaction under the weak base condition of potassium carbonate (K ₂ CO ₃ ) to form nitrogen (N). a phenylated product ( 1 ) having a phenyl group.

Nuclear magnetic resonance spectrum ( ¹ H NMR, 300 MHz, CDCl ₃ ) of phenylated product ( 1 ): δ 8.16-8.13 (m, 2H), 7.63 - 7.54 (m, 2H), 7.51-7.40 (m, 5H) And 7.38-7.24 (m, 4H).

Second process

In the monohalogenation reaction (see the second scheme), the phenylated product ( 1 ) is subjected to a single bromine substitution reaction under the action of N-bromosuccinimide (NBS) to form a bromine at position 3 Monohalogenated product ( 2 ).

Third process

In the aromatic thiol substitution reaction (see Scheme 3), the monohalogenated product ( 2 ) is substituted with diphenyl disulfide under the action of n-butyllithium (n-BuLi) to form No. 3 The first thioether product ( 3 ) in the position of a thioether group.

Fourth process

In the sulfur bond oxidation reaction (see the fourth scheme), the sulfur bond of the first sulfide product ( 3 ) is subjected to an oxidation reaction under the action of m-chloroperoxybenzoic acid to form a carbazole derivative Cbz1.

Nuclear magnetic resonance spectroscopy ( ¹ H NMR, 400 MHz, DMSO) of the carbazole derivative Cbz1: δ 9.0 (d, 1H), 8.5 (d, 1H), 8.01 (q, 2H), 7.97 (d, 1H), 7.7 (t, 3H), 7.56 (m, 7H) and 7.37 (q, 2H).

Fig. 1 is an absorption or excitation spectrum of the carbazole derivative Cbz1 in which the horizontal axis is the wavelength (nm) and the vertical axis is the normalized intensity. As can be seen from Fig. 1, the maximum absorption wavelength (-x-) of the carbazole derivative Cbz1 is 283 and 325 nm, the excitation wavelength at room temperature (-Δ-) is 350 and 367 nm, and the maximum excitation wavelength is 77 K. (-) is 408 and 436 nm.

Further, from the curve distribution of Fig. 1, it is understood that the overlap ratio of the absorption spectrum (-x-) of the carbazole derivative Cbz1 to the room temperature excitation spectrum (-?-) is less than 3%, and the absorption spectrum (-x-) and The overlap rate of the maximum excitation wavelength (-) at a temperature of 77 K approaches 0%. The above results indicate that the absorption ratio of the absorption spectrum of the carbazole derivative Cbz1 to the emission spectrum is extremely low, so that the absorbed light can be efficiently converted into excitation light.

Example 2: Carbazole derivative Cbz2

Here, a carbazole derivative Cbz2 and a method for producing the same are provided, and the carbazole derivative Cbz2 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbz2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbz2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbz2 was obtained by the above reaction process.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step.

Fifth process

In the double halogenation process (see Scheme 5), the phenylation product ( 1 ) is brominated with bromine water (Br ₂ ) under acidic conditions of acetic acid (CH ₃ COOH) to form Nos. 3 and 6. The position is the first double halogenated product of bromine ( 4 ).

The first halogenated product bis (4) Proton NMR ^{(1 H NMR, 300 MHz,} CDCl 3): δ 8.20 (d, 2H), 7.64-7.59 (m, 2H), 7.52-7.48 (m, 5H) , 7.27 (s, 1H) and 7.25 (s, 1H).

Sixth process

In the aromatic thiol group substitution reaction (see Scheme 6), the first bishalogenated product ( 4 ) and diphenyl disulfide (Ph ₂ S) are treated with n-butyllithium (n-BuLi). ₂ ) A substitution reaction is carried out to form a second sulfide product ( 5 ) having a thioether group at positions 3 and 6.

Nuclear magnetic resonance spectrum of the second sulfide product ( 5 ) ( ¹ H NMR, 300 MHz, CDCl ₃ ): δ 8.26 (d, 2H), 7.66-7.50 (m, 10H), 7.41-7.38 (m, 2H) , 7.27-7.18 (m, 5H) and 7.16-7.11 (m, 2H); ESI-MS: [M+1] ⁺ = 460.

7th process

In the sulfur bond oxidation reaction (see Scheme 7), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (molar ratio m -CPBA: ( 5) = 4:1), let the second The sulfur bond of the thioether product ( 5 ) undergoes an oxidation reaction to form a carbazole derivative Cbz2.

Nuclear magnetic resonance spectrum of the carbazole derivative Cbz2 ( ¹ H NMR, 400 MHz, DMSO): δ 9.32 (d, 2H), 8.04 (m, 6H), 7.64 (m, 11H) and 7.48 (d, 2H).

Fig. 2 is an absorption or excitation spectrum of the carbazole derivative Cbz2 in which the horizontal axis is the wavelength (nm) and the vertical axis is the normalized intensity. As can be seen from Fig. 2, the maximum absorption wavelength (-x-) of the carbazole derivative Cbz2 is 284 and 312 nm, the excitation wavelength at room temperature (-Δ-) is 349 and 367 nm, and the maximum excitation wavelength is 77 K. (-) is 403 and 435 nm.

Further, from the curve distribution of Fig. 2, the overlap ratio of the absorption spectrum (-x-) of the carbazole derivative Cbz2 to the room temperature excitation spectrum (-?-) is less than 1%, and the absorption spectrum (-x-) and The overlap rate of the maximum excitation wavelength (-) at a temperature of 77 K approaches 0%. The above results indicate that the absorption ratio of the absorption spectrum of the carbazole derivative Cbz2 to the emission spectrum is extremely low, so that the absorbed light can be efficiently converted into excitation light.

Example 3: Carbazole derivative Cbbso2

Here, a carbazole derivative Cbbso2 and a method for producing the same are provided, and the carbazole derivative Cbbso2 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbbso2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbbso2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbbso2 was obtained by the above reaction process.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step. In the double halogenation process, the first bishalogenated product ( 4 ) having bromine positions 3 and 6 was obtained by the method described in the above fifth scheme. In the aromatic thiol group substitution reaction, a second thioether product ( 5 ) having a thioether group at positions 3 and 6 is obtained by the method described in the above sixth scheme.

The eighth process

In the sulfur bond oxidation reaction (see Scheme 8), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (moire number ratio m -CPBA: ( 5) = 2:1), let the second The sulfur bond of the thioether product ( 5 ) undergoes an oxidation reaction to form a carbazole derivative Cbbso2.

The carbazole derivative Cbbso2 H NMR ^{(1 H NMR, 300 MHz,} CDCl 3): δ 8.52 (t, 2H), 7.71-7.57 (m, 10H) , and 7.51-7.37 (m, 9H); ESI- MS: [M+1] ⁺ = 514.

Example 4: Carbazole derivative Cbps2

Here, a carbazole derivative Cbps2 and a method for producing the same are provided, and the carbazole derivative Cbps2 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbps2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbps2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbps2 was obtained by the above reaction process.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step. In the double halogenation process, the first bishalogenated product ( 4 ) having bromine positions 3 and 6 was obtained by the method described in the above fifth scheme.

9th process

In the aromatic thiol group substitution reaction (see Scheme 9), the first bishalogenated product ( 4 ) is subjected to a substitution reaction with dipyridyl disulfide under the action of n-butyllithium (n-BuLi). A third thioether product ( 6 ) having a thioether group at positions 3 and 6 is formed.

Nuclear magnetic resonance spectrum of the third sulfide product ( 6 ) ( ¹ H NMR, 300 MHz, CDCl ₃ ): δ 8.4 (d, 4H), 7.66 (d, 2H), 7.63-7.51 (m, 5H), 7.29 (d, 2H), 7.42-7.37 (m, 2H), 7.70-6.93 (m, 2H), and 6.83-6.80 (t, 2H); ESI-MS: [M+1] ⁺ = 463.

10th process

In the sulfur bond oxidation reaction (see process 10), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (moire number ratio m -CPBA: ( 6) = 4:1), let the third The sulfur bond of the thioether product ( 6 ) undergoes an oxidation reaction to form a carbazole derivative Cbps2.

The carbazole derivative Cbps2 H NMR ^{(1 H NMR, 300 MHz,} CDCl 3): δ 8.91 (d, 2H), 8.70 (d, 2H), 8.31 (d, 2H), 8.20 (dd, 2H) 7.96 (m, 2H), 7.68-7.55 (m, 4H) and 7.42-7.39 (m, 5H); ESI-MS: [M+1] ⁺ = 526.

real Example 5: Carbazole derivative Cbpso2

Here, a carbazole derivative Cbpso2 and a process for producing the same are provided, and the carbazole derivative Cbpso2 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbpso2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbpso2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbpso2 was obtained by the above reaction process.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step. In the double halogenation process, the first bishalogenated product ( 4 ) having bromine positions 3 and 6 was obtained by the method described in the above fifth scheme. In the aromatic thiol group substitution reaction, a third thioether product ( 6 ) having a thioether group at positions 3 and 6 is obtained by the method described in the above ninth scheme.

11th process

In the sulfur bond oxidation reaction (see step 11), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (moire number m- CPBA: ( 6) = 2:1), let the third The sulfur bond of the thioether product ( 6 ) undergoes an oxidation reaction to form a carbazole derivative Cbpso2.

Nuclear magnetic resonance spectroscopy of the carbazole derivative Cbpso2 ( ¹ H NMR, 300 MHz, CDCl ₃ ): δ 8.60 (dd, 2H), 8.54-8.50 (m, 2H), 8.18-8.12 (m, 2H), 7.91 7.88 (m, 2H), 7.82-7.78 (m, 2H), 7.60-7.44 (m, 3H), 7.42-7.36 (m, 4H) and 7.30-7.25 (m, 2H); ESI-MS: [M+ 1] ⁺ =494.

Example 6: Carbazole derivative CbbCls2

Here, a carbazole derivative CbbCls2 and a method for producing the same are provided, and the carbazole derivative CbbCls2 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative CbbCls2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative CbbCls2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. By the above reaction process, the carbazole derivative CbbCls2 was obtained.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step. In the double halogenation process, the first bishalogenated product ( 4 ) having bromine positions 3 and 6 was obtained by the method described in the above fifth scheme.

12th process

In the aromatic thiol group substitution reaction (see Scheme 12), the first bishalogenated product ( 4 ) and di-p-chlorophenyl disulfide are replaced by n-butyllithium (n-BuLi). The reaction forms a fourth sulfide product ( 7 ) having a thioether group at positions 3 and 6.

Nuclear magnetic resonance spectrum of the fourth sulfide product ( 7 ) ( ¹ H NMR, 300 MHz, CDCl ₃ ): δ 7.67-7.62 (m, 2H), 7.57-7.50 (m, 5H), 7.40 (d, 2H) And 7.21 - 7.11 (m, 8H); ESI-MS: [M+1] ⁺ = 528.

13th process

In the sulfur bond oxidation reaction (see Scheme 13), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (moire number ratio m -CPBA: ( 7) = 6:1), let the fourth The sulfur bond of the thioether product ( 7 ) undergoes an oxidation reaction to form a carbazole derivative CbbCls2.

The carbazole derivative CbbCls2 H NMR ^{(1 H NMR, 300 MHz,} CDCl3): δ 8.80 (d, 2H), 8.02-7.93 (m, 6H), 7.67-7.58 (m, 3H) and 7.51-7.41 (m, 8H); ESI-MS: [M+1] ⁺ = 592.

Example 7: Carbazole derivative CbbClso2

Here, a carbazole derivative CbbClso2 and a method for producing the same are provided, and the carbazole derivative CbbClso2 can be used as a main luminescent material of an organic light-emitting diode. The structure of the above carbazole derivative CbbClso2 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative CbbClso2 comprises an N-phenylation reaction of carbazole, a bishalogenation reaction of carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. By the above reaction process, the carbazole derivative CbbClso2 was obtained.

In the N-phenylation reaction, a phenylated product ( 1 ) having a phenyl group at a nitrogen (N) position is obtained by the method described in the above first step. In the double halogenation process, the first bishalogenated product ( 4 ) having bromine positions 3 and 6 was obtained by the method described in the above fifth scheme. In the aromatic thiol group substitution reaction, the fourth sulfide product ( 7 ) having a thioether group at positions 3 and 6 is obtained by the method described in the above-mentioned 12th step.

14th process

In the sulfur bond oxidation reaction (see step 14), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (molar ratio m -CPBA: ( 7) = 3:1), let the fourth The sulfur bond of the thioether product ( 7 ) undergoes an oxidation reaction to form a carbazole derivative CbbClso2.

Nuclear magnetic resonance spectroscopy of the carbazole derivative CbbClso2 ( ¹ H NMR, 300 MHz, CDCl ₃ ): δ 8.81 (d, 2H), 8.49-7.51 (m, 6H), 7.49-7.41 (m, 3H) and 7.39- 7.37 (m, 8H); ESI-MS: [M+1] ⁺ = 560.

Table 1 shows the maximum absorption wavelength, the maximum excitation wavelength, and the excited triplet state (T ₁ ) of the above seven carbazole derivatives. As is clear from the results of Table 1, the difference between the maximum absorption wavelength and the maximum excitation wavelength of the above seven carbazole derivatives was 28 to 95 nm, and the T ₁ value was 3.00 to 3.05 electron volts (eV).

Wherein, when the T ₁ value of the main luminescent material is greater than 2.8 eV, the luminous efficiency of the main luminescent material is better. Compared with the conventional main illuminant material TcTa, the T ₁ value is 2.7, and the above carbazole derivatives have T ₁ values of more than 2.8 eV, and thus have better luminous efficiency.

Example 8: Carbazole derivative Cbz3

Here, a carbazole derivative Cbz3 and a method for producing the same are provided, and the carbazole derivative Cbz3 can be used as a main illuminant material of an organic light-emitting diode. The structure of the above carbazole derivative Cbz3 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative Cbz3 comprises an N-biphenylation reaction of a carbazole, a bishalogenation reaction of a carbazole, an aromatic thiol group substitution reaction, and a sulfur bond oxidation reaction. The carbazole derivative Cbz3 was obtained by the above reaction process.

15th process

In the N-biphenylation reaction (see Scheme 15), the carbazole and iodobenzene are subjected to a two-molecule nucleophilic substitution reaction under the weak base condition of potassium carbonate (K ₂ CO ₃ ) to form nitrogen ( N) a biphenylated product ( 8 ) having a biphenyl group.

Nuclear magnetic resonance spectrum ( ¹ H NMR, 300 MHz, CDCl ₃ ) of the biphenylated product ( 8 ): δ 8.16 (d, 2H, J = 7.5 Hz), 7.83 (d, 2H, J = 8.7 Hz), 7.68 (dd, 4H, J = 9 Hz, 12 Hz) and 7.54 - 7.33 (m, 9H); ESI-MS: [M+1] ⁺ = 319.

16th process

In the double halogenation reaction (see the 16th process), the biphenylated product ( 8 ) is brominated with bromine water (Br ₂ ) under acidic conditions of acetic acid (CH ₃ COOH) to form No. 3 and Position 6 is the second bishalogenated product of bromine ( 9 ).

Nuclear magnetic resonance spectrum ( ¹ H NMR, 300 MHz, CDCl ₃ ) of the second bishalogenated product ( 9 ): δ 8.20 (d, 2H, J = 1.8 Hz), 7.81 (d, 2H, J = 8.1 Hz), 7.67 (d, 2H, J = 7.8 Hz) and 7.57-7.29 (m, 9H); ESI-MS: [M+1] ⁺ = 477.

17th process

In the aromatic thiol group substitution reaction (see Scheme 17), the second bishalogenated product ( 9 ) and diphenyl disulfide (Ph ₂ S) are treated with n-butyllithium (n-BuLi). ₂ ) A substitution reaction is carried out to form a fifth sulfide product ( 10 ) having a thioether group at positions 3 and 6.

Nuclear magnetic resonance spectrum ( ¹ H NMR, 300 MHz, CDCl ₃ ) of the fifth sulfide product ( 10 ): δ 8.26 (d, 2H, J = 1.5 Hz), 7.84 (d, 2H, J = 6.9 Hz), 7.68-7.42 (m, 9H) and 7.24-7.12 (m, 10H); ESI-MS: [M+1] ⁺ = 535.

18th process

In the sulfur bond oxidation reaction (see the 18th process), under the action of m -chloroperoxybenzoic acid ( m- CPBA) (moire number ratio m -CPBA: ( 10) = 4:1), let the fifth The sulfur bond of the thioether product ( 10 ) undergoes an oxidation reaction to form a carbazole derivative Cbz3.

The carbazole derivative Cbz3 H NMR ^{(1 H NMR, 300 MHz,} CDCl 3): δ 8.82 (d, 2H, J = 1.2 Hz), 8.06-7.85 (m, 9H), 7.38 (d, 2H, J = 8.4 Hz), 7.66 (d, 2H, J = 8.4 Hz) and 7.58-7.42 (m, 10H); ESI-MS: [M+1] ⁺ = 599.

Example 9: Carbazole derivative FYL-B41

Here, a carbazole derivative FYL-B41 and a method for producing the same are provided, and the carbazole derivative FYL-B41 can be used as a main luminescent material of an organic light-emitting diode. The structure of the above carbazole derivative FYL-B41 is as shown in the following chemical formula:

According to an embodiment of the present invention, a method for producing a carbazole derivative FYL-B41 comprises a guanidinium sulfate substitution reaction and a dicarbazole substitution reaction. The carbazole derivative FYL-B41 was obtained by the above reaction process.

19th process

In the hydrazine sulfate substitution reaction (see Scheme 19), 1,2-bis(4'-bromophenyl)ethanedione and sulfuric acid were obtained under alkaline conditions of triethylamine (Et ₃ N). Guanamine The substitution reaction is carried out to form a guanidinium sulfate substituted product ( 11 ) having a thiadiazole group.

Ammonium sulfate substituted acyl product (11) Proton NMR ^{(1 H NMR, 300 MHz,} CDCl 3): δ 7.64 (d, 4H, J = 6.0 Hz) and 7.44 (d, 4H, J = 8.7 Hz); ESI-MS: [M+1] ⁺ = 428.

20th process

In the dicarbazole substitution reaction (see Scheme 20), the hydrazine sulfate substituted product ( 11 ) is subjected to a substitution reaction with carbazole under the catalysis of copper iodide (CuI) (molar ratio carbazole: ( 11) = 2.5: 1), a carbazole derivative FYL-B41 having a dicarbazole group is formed.

FYL-B41 carbazole derivative spectra of proton nuclear magnetic resonance ^{(1 H NMR, 300 MHz,} CDCl 3): δ 8.14 (dd, 4H, J = 1.8 Hz, 7.2 Hz), 7.66 (dd, 4H, J = 1.8 Hz , 7.2 Hz), 7.50-7.44 (m, 4H), 7.42-7.36 (m, 4H), 7.32-7.28 (m, 4H) and 7.11-7.06 (m, 4H); ESI-MS: [M+1] ⁺ =600.

Application of carbazole derivatives in organic light-emitting diodes

Since the above carbazole derivative can be used as the main illuminant material of the organic light-emitting diode, the above-described carbazole derivative is used in the following examples to produce an organic light-emitting diode.

The structure of the above organic light-emitting diode is as shown in Fig. 3. In FIG. 3, the structure of the organic light emitting diode 100 includes a first electrode 110 and a second electrode 120 opposite to the first electrode 110, and a hole transmission disposed between the first electrode 110 and the second electrode 120. The layer 130 and the electron transport layer 140 opposite to the hole transport layer 130 and the light emitting layer 150 disposed between the hole transport layer 130 and the electron transport layer 140. The luminescent layer 150 includes a main illuminant material and a guest illuminant material, wherein the main illuminant material may be a carbazole derivative as described above.

Example 10

Embodiment 10 provides an organic light-emitting diode having a structure as shown in FIG. The first electrode 110 is an indium tin oxide (ITO) substrate, the second electrode 120 is aluminum-lithium fluoride (Al/LiF), and the hole transport layer 130 is a hole transport material AUS HIL and 4, 4', 4 "-Tris(9-carbazolyl)triphenylamine (TcTa), the electron transport layer 140 is tris(8-hydroxyquinoline)aluminum (Alq ₃ ), and the luminescent layer 150 is a carbazole derivative Cbz1 and bis (3, 5-Difluorophenylpyridinyl)-(2-carboxypyridinyl)phosphonium (III) (FIrpic) was mixed.

The main illuminant material of the luminescent layer composition is carbazole derivative Cbz1, and the guest illuminant material is bis(3,5-difluorophenylpyridyl)-(2-carboxypyridyl) ruthenium (III) (FIrpic) ). The percentage by weight of the main illuminant material and the guest illuminant material is, for example, four times or more, and the weight concentration percentage of the guest illuminant material is substantially not equal to zero.

Example 11

Embodiment 11 provides an organic light-emitting diode having a structure as shown in FIG. The first electrode 110 is an indium tin oxide (ITO) substrate, the second electrode 120 is aluminum-lithium fluoride (Al/LiF), and the hole transport layer 130 is a hole transport material AUS HIL and 4, 4', 4 "-Tris(9-carbazolyl)triphenylamine (TcTa), the electron transport layer 140 is tris(8-hydroxyquinoline)aluminum (Alq ₃ ), and the luminescent layer 150 is a carbazole derivative Cbz2 and bis (3, 5-Difluorophenylpyridinyl)-(2-carboxypyridinyl)phosphonium (III) (FIrpic) was mixed.

The main illuminant material of the luminescent layer composition is carbazole derivative Cbz1, and the guest illuminant material is bis(3,5-difluorophenylpyridyl)-(2-carboxypyridyl) ruthenium (III) (FIrpic) ). The percentage by weight of the main illuminant material and the guest illuminant material is, for example, four times or more, and the weight concentration percentage of the guest illuminant material is substantially not equal to zero.

Table 2 compares the effects of different main illuminant materials on the luminescence intensity and external quantum efficiency of organic light-emitting diodes (OLEDs). In the examples 10 and 11, respectively, Cbz1 and Cbz2 are the main illuminant materials, and in the comparative example, the conventional TcTa is the main illuminant material. From the results of Table 2, the luminescence intensity of Example 10 and Example 11 was significantly better than that of the comparative example (≧26.5 cd/A), and the external quantum efficiency (EQE) was also significantly better. (≧13%).

The primary illuminant material provided by one aspect of the present invention has better hole transporting ability, and because its T ₁ value is greater than 2.8 eV, the external quantum efficiency is increased, so that the luminescence intensity is significantly increased. Therefore, the above-mentioned main illuminant material is a preferred solution to the conventional technical problems, and can be directly applied to the phosphorescent luminescent layer of the organic light-emitting diode.

The preferred embodiments of the present invention are disclosed as described above, however, the illustrated manufacturing methods are not limited to the embodiments of the present invention. Various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

100. . . Organic light-emitting diode

110. . . First electrode

120. . . Second electrode

130. . . Hole transport layer

140. . . Electronic transport layer

150. . . Luminous layer

Figure 1 is the absorption or excitation spectrum of the carbazole derivative Cbz1, wherein the horizontal axis is the wavelength (nm) and the vertical axis is the normalized intensity, wherein the maximum absorption wavelength (-x-) of the carbazole derivative Cbz1, room temperature excitation wavelength (-△-), and the maximum excitation wavelength (-) at a temperature of 77 K.

Figure 2 is the absorption or excitation spectrum of the carbazole derivative Cbz2, wherein the horizontal axis is the wavelength (nm) and the vertical axis is the normalized intensity, wherein the maximum absorption wavelength (-x-) of the carbazole derivative Cbz2, room temperature excitation wavelength (-△-), and the maximum excitation wavelength (-) at a temperature of 77 K.

3 is a schematic view showing the structure of an organic light-emitting diode 100 according to an aspect of the present invention.

100. . . Organic light-emitting diode

110. . . First electrode

120. . . Second electrode

130. . . Hole transport layer

140. . . Electronic transport layer

150. . . Luminous layer

Claims (11)

A host material which is a carbazole derivative having the following chemical formula (I): Wherein R ₁ and R ₂ are independently hydrogen or And at least one of R ₁ and R ₂ is X is a sulfur linkage (-S-), a sulfoxide linkage (-SO-) or a sulfone linkage (-SO ₂ -), Y is carbon or nitrogen, and R ₄ is hydrogen. Fluorine, chlorine, bromine, iodine, C1-C30 alkyl, C1-C30 alkanol or aryl substituent, n is an integer from 0 to 2, and , whose R ₅ is hydrogen or , R ₆ is R ₄ or , R ₄ and n are the same as described above. The primary illuminant material of claim 1, wherein R ₁ of the formula (I) is hydrogen, or R ₁ is When n = 0, X is an arylene bond (-SO-) or a hydrazone bond (-SO ₂ -), R ₄ is hydrogen or chlorine, and R ₂ of the formula (I) is When n = 0, X is an arylene bond (-SO-) or a hydrazone bond (-SO ₂ -), R ₄ is hydrogen or chlorine, and R ₃ of the formula (I) is When n=0, and R ₄ and R ₅ are hydrogen, the structure of the main illuminant material is one of the following chemical structural formulas: The primary illuminant material of claim 1, wherein R ₁ and R ₂ of the formula (I) are When n = 0, R ₄ is hydrogen, X is a hydrazone bond (-SO ₂ -), Y is carbon, and R ₃ of the formula (I) is When the primary illuminant material has the following chemical structural formula: The primary illuminant material of claim 1, wherein R ₁ and R ₂ of the formula (I) are When n = 0, Y is carbon, and R ₃ of the formula (I) is When n=0, R ₅ is When R ₆ is R ₄ , the structure of the main illuminant material is the following chemical formula (II): The primary illuminant material of claim 1, wherein R ₁ and R ₂ of the formula (I) are When n = 0, Y is carbon, and R ₃ of the formula (I) is When n=0, R ₅ is And R ₆ is The structure of the main illuminant material is the following chemical formula (III): The primary illuminant material of claim 1, wherein R ₁ and R ₂ of the formula (I) are When Y is carbon, and R ₃ of the formula (I) is When n is an integer from 0 to 2, the structure of the main illuminant material is the following chemical formula (IV): The host material according to claim 1, wherein R ₁ and R ₂ of the formula (I) are R ₄ , and R ₃ of the formula (I) is The structure of the main illuminant material is the following chemical formula (V): The main illuminant material according to claim 7, wherein when the R ₄ of the formula (V) is hydrogen, the structure of the main illuminant material is as shown in the following chemical structural formula: An organic light emitting diode comprising: a first electrode and a second electrode opposite to the first electrode; a hole transport layer and an electron transport layer opposite to the hole transport layer, wherein the hole transport a layer and the electron transport layer disposed between the first electrode and the second electrode; and a light emitting layer disposed on the hole transport layer and the electron transport layer The luminescent layer comprises a primary illuminant material and a guest illuminant material, as described in any one of claims 1 to 8. The organic light-emitting diode according to claim 9, wherein the guest illuminant is bis(3,5-difluorophenylpyridyl)-(2-carboxypyridyl)iridium (III) (FIrpic), double ( 3,5-Difluorophenylpyridyl)tetrakis(1-pyrazolyl)borate (III) (FIr6), bis(3,5-difluorophenylpyridyl)-5-(2-pyridyl) -1 hydrogen-tetrazolium (III) (FIrN4), bis(3,5-difluorophenylpyridinyl)-3-(trifluoromethyl)-5-(2-pyridyl)-1,2, 4-triazolium (III) (FIrtaz), tris(2-phenylpyridyl)ruthenium (III) (Irppy3), bis(2-phenylquinolinyl)(acetoxime) ruthenium (III) (PQIr Or, tris(1-phenylisoquinolinyl)iridium (III) (Irpiq). The organic light-emitting diode according to claim 10, wherein the percentage of the weight concentration of the main illuminant material and the guest illuminant material is 4 times or more, and the weight concentration percentage of the guest illuminant material is not 0.