TW201930297A - Carbazole-substituted triazine compounds and organic electroluminescent devices using the same - Google Patents

Abstract

The present invention provides a carbazole-substituted triazine compounds of formula (I) and an organic electroluminescent device using the same: wherein Ar1, L, Z1, X1, m and n are as defined in the description.

Description

Carbazole-substituted triazine compound and its organic electroluminescent device

The present invention relates to a material for an organic electroluminescent device and an organic electroluminescent device using the same, and more particularly to a material capable of improving the performance of the device and an organic electroluminescent device using the material.

Organic electroluminescent devices (OLEDs) are regarded as the most promising flat display technology due to their characteristics of lightness, thinness, wide viewing angle, high contrast, low power consumption, high response speed, full color, and flexibility. In order to satisfy the application of the organic electro-excitation light element, the development of novel organic materials is particularly emphasized.

A typical OLED is a multilayer thin film structure formed by sequentially depositing an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode by a vacuum deposition method or a coating method. When a current is applied, the anode injects holes and the cathode injects electrons into the one or more organic layers, and the injected holes and electrons each migrate to the opposite charged electrode. When electrons and holes are confined to the same molecule, an "exciton" is formed. The exciton system has a limited electron-hole pair with excited energy states, and the excitons relax to emit light through a light-emitting mechanism. .

The multi-layer thin film structure of OLED is to provide good element efficiency and long service life. The key considerations include the stability of the interface between the electrodes and the organic layer and the combination of a commensurate organic layer. Holes and electrons can be effectively transmitted to the light-emitting layer, so that the density of the electrons and holes in the light-emitting layer is balanced, and the light-emitting efficiency is increased. It has been published in the literature that the way in which the host material is blended with another guest material can also improve component performance and adjust chromaticity. Several OLED materials and device configurations are described in US Patent Nos. 4,796,292, 5,844,363, 5,707,745, 6,596,415, and 6,465,115, which are incorporated herein by reference in their entirety.

It is known that the introduction of carbazole compounds has the benefit of balancing electron and hole mobility. However, its carbazole compounds tend to make the band gap smaller, making the performance of OLED devices difficult to meet the needs of practical display applications, especially for For automotive displays, the organic materials used in organic electroluminescent devices need to have good thermal stability in order to maintain their light emission chromaticity and luminous efficiency requirements.

Therefore, there is an urgent need for an organic material with good heat resistance, which can significantly improve the performance of organic electro-optical light-emitting elements to meet the needs of diverse applications.

An object of the present invention is to provide a material for an organic electroluminescent device having a density balance of the electrons and holes in the light emitting layer, improved luminous efficiency, and excellent heat resistance.

The present invention provides a carbazole-substituted triazine compound having the structure of formula (I):

Among them, Ar _{1 is} each the same or different, and each Ar ₁ independently represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _6-30 aryl, and substituted or unsubstituted A C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; m represents an integer of 1 or 2; n represents an integer of 0 to 2; wherein n is 0 , L represents a substituted or unsubstituted C _5-12 aryl group, and a substituted or unsubstituted C _3-40 containing at least one heteroatom selected from the group consisting of N, O, and S Heteroaryl; and when n is 1 or 2, L represents a substituted or unsubstituted C _5-12 arylene group, and the substituted or unsubstituted group contains a member selected from the group consisting of N, O, and S At least one hetero atom of C _3-40 heteroaryl; Z ₁ represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _5-12 aryl, and substituted or unsubstituted A substituted C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; and X ₁ is a structure of formula (I-1) or formula (I-2) : Among them, G represents a single bond, C atom, O atom, or S atom; B represents hydrogen, substituted or unsubstituted C containing at least one heteroatom selected from the group consisting of N, O, and S _3-10 heteroaryl or substituted or unsubstituted C _6-12 bicyclic ring fused with a compound of formula (I-1); R ₁ each independently represents hydrogen or C _1-4 alkyl; R ₂ , R ₃ Are the same or different and each R ₂ and R ₃ independently represent hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from the group consisting of N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group of S; and f represents an integer of 0 to 2.

The present invention further provides an organic electro-optic light-emitting element, comprising: a cathode; an anode; and an organic layer interposed between the cathode and the anode, and the organic layer includes the carbazole-substituted structure having the above formula (I). Triazine compounds.

According to the present invention, the carbazole-substituted triazine compound having the formula (I) structure provided by the present invention can effectively balance the density of electrons and holes in the light-emitting layer, and improve the current efficiency and Provides the benefits of good heat resistance.

100, 200, 300‧‧‧ organic electro-excitation light elements

110, 210, 310‧‧‧ substrate

120, 220, 320‧‧‧ Anode

130, 230, 330‧‧‧ Hole injection layer

140, 240, 340‧‧‧hole transmission layer

150, 250, 350‧‧‧ luminescent layers

160, 260, 360‧‧‧ electron transmission layer

170, 270, 370‧‧‧ electron injection layer

180, 280, 380‧‧‧ cathode

245, 355‧‧‧ exciton blocking layer

The embodiment of the present invention will be described by way of example with reference to the accompanying drawings: FIG. 1 is a schematic cross-sectional view of an embodiment of an organic electroluminescent device according to the present invention; FIG. 2 is another implementation of the organic electroluminescent device according to the present invention Example is a schematic cross-sectional view; and FIG. 3 is a schematic view of another embodiment of the organic electro-optical light emitting device of the present invention. Schematic cross-section.

The following is a description of specific embodiments of the present invention. Those skilled in the art can easily understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied by other different embodiments, and various details in this specification can also be given different modifications and changes based on different viewpoints and applications without departing from the spirit disclosed by the present invention. In addition, all ranges and values herein are inclusive and combinable. Any value or point that falls within the range described herein, for example, any integer can be used as the minimum or maximum value to derive the lower range, etc.

According to the present invention, a carbazole-substituted triazine compound having the structure of formula (I):

Among them, Ar _{1 is} each the same or different, and each Ar ₁ independently represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _6-30 aryl, and substituted or unsubstituted A C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; m represents an integer of 1 or 2; n represents an integer of 0 to 2; wherein n is 0 , L represents a substituted or unsubstituted C _5-12 aryl group, and a substituted or unsubstituted C _3-40 containing at least one heteroatom selected from the group consisting of N, O, and S Heteroaryl; and when n is 1 or 2, L represents a substituted or unsubstituted C _5-12 arylene group, and the substituted or unsubstituted group contains a member selected from the group consisting of N, O, and S At least one hetero atom of C _3-40 heteroaryl; Z ₁ represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _5-12 aryl, and substituted or unsubstituted A substituted C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; and X ₁ is a structure of formula (I-1) or formula (I-2) : Among them, G represents a single bond, C atom, O atom, or S atom; B represents hydrogen, substituted or unsubstituted C containing at least one heteroatom selected from the group consisting of N, O, and S _3-10 heteroaryl or substituted or unsubstituted C _6-12 bicyclic ring fused with a compound of formula (I-1); R ₁ each independently represents hydrogen or C _1-4 alkyl; R ₂ , R ₃ Are the same or different and each R ₂ and R ₃ independently represent hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from the group consisting of N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group of S; and f represents an integer of 0 to 2.

In a specific embodiment, the carbazole-substituted triazine compound having the structure of the formula (I) is represented by the structure of the formula (II):

Among them, Ar _{1 is} each the same or different, and each Ar ₁ independently represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _6-30 aryl, substituted or unsubstituted C _3-40 heteroaryl containing at least one heteroatom selected from the group consisting of N, O, and S; m represents an integer of 1 or 2; n represents an integer of 0 to 2; when n is 0, L Represents a substituted or unsubstituted C _5-12 aryl group, a substituted or unsubstituted C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; When n is 1 or 2, L represents substituted or unsubstituted C _5-12 arylene, substituted or unsubstituted containing at least one heteroatom selected from the group consisting of N, O, and S C _3-40 heteroaryl; Z ₁ represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _5-12 aryl, substituted or unsubstituted containing selected from N A C _3-40 heteroaryl group of at least one heteroatom in the group consisting of, O, and S; and X ₁ represents a structure of formula (I-1) or formula (I-2): Among them, G represents a single bond, C atom, O atom, or S atom; B represents hydrogen, substituted or unsubstituted C containing at least one heteroatom selected from the group consisting of N, O, and S _3-10 heteroaryl or substituted or unsubstituted C _6-12 bicyclic ring fused with a compound of formula (I-1); R ₁ each independently represents hydrogen or C _1-4 alkyl; R ₂ , R ₃ Are the same or different and each R ₂ and R ₃ independently represent hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from the group consisting of N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group of S; and f represents an integer of 0 to 2.

In the text, "substituted" expressed as "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced with another atom or group (ie, a substituent). The substituents are each independently selected from at least one of the group consisting of: deuterium, halogen, C _1-30 alkyl, C _1-30 alkoxy, C _6-30 aryl, C _{5- 30} heteroaryl, C _5-30 heteroaryl substituted with C _6-30 aryl, benzimidazolyl, C _3-30 cycloalkyl, C _5-7 heterocycloalkyl, tri-C _1-30 alkane Silyl, tri-C _1-30 aryl silyl, di-C _1-30 alkyl, C _6-30 aryl silyl, C _1-30 alkyl, di C _6-30 aryl silyl, C _2-30 Alkenyl, C _2-30 alkynyl, cyano, di C _1-30 alkylamino, di C _{6-30 arylboryl} , di C _{1-30 alkylboryl} , C _1-30 alkyl, C _6-30 aryl C _1-30 alkyl, C _1-30 alkyl C _6-30 aryl, carboxyl, nitro and hydroxyl.

In the text, "aryl" means aryl or (extended) aryl, which refers to a monocyclic ring or fused polycyclic ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, bitriphenyl, Naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenphenanthryl, anthryl, indenyl, Triphenylene, fluorenyl, fused tetraphenyl, fluorenyl, fluorenyl, naphthylnaphthyl, allenyl fluorenyl and the like.

Herein, "heteroaryl" means heteroaryl or (extended) heteroaryl, which refers to a ring main chain atom containing at least one heteroatom selected from the group consisting of N, O, and S. Aryl, which may be a monocyclic ring, such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, iso Oxazolyl, Oxazolyl, Diazolyl, Tris Base, four , Triazolyl, tetrazolyl, furyl, pyridyl, pyridyl Base, pyrimidinyl, Or a fused ring condensed with at least one benzene ring, such as benzofuryl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, Benzothiazolyl, Benzoisothiazolyl, Benzoiso Oxazolyl, quinolinyl, isoquinolinyl, fluorenyl, quinazolinyl, quinol Phenyl, carbazolyl, brown Oxazolyl, morphinyl, benzobis Uhyl, dihydroacridyl, etc.

In a specific embodiment, B represents a substituted C _6-12 bicyclic ring fused to a compound of formula (I-1), and the substituent is a C _1-4 alkyl group.

X ₁ of the carbazole-substituted triazine compound having the formula (I) is selected from one of the following groups:

In a specific embodiment, when the carbazole-substituted triazine compound having the structure of formula (I) is n, L is selected from substituted or unsubstituted phenyl, biphenyl, or Pyrimidinyl; when n is 1 or 2, L is selected from substituted or unsubstituted phenylene, phenylene or pyrimidinyl.

In a specific embodiment, Z ₁ of the carbazole-substituted triazine compound having the structure of formula (I) is a substituted triazine group. For example, when Z ₁ is triazinyl, it may be substituted with two phenyl groups.

In a specific embodiment, when the carbazole-substituted triazine compound having the structure of formula (I) is 1 and n is 0, L is phenyl.

In another embodiment, the preferred embodiment of the carbazole-substituted triazine compound having the structure of formula (I) when m is 1 and n is 0 is a compound selected from Table 1, but is not limited thereto. this.

In another embodiment, the carbazole-substituted triazine compound is particularly preferably the compound (1-2).

In a specific aspect, when m is 1 and n is 1, the carbazole-substituted triazine compound having the structure of formula (I) is selected from the group consisting of unsubstituted Phenylene, or unsubstituted phenylene.

In another embodiment, the preferred embodiment of the carbazole-substituted triazine compound having the structure of formula (I), when m is 1 and n is 1, is a compound selected from Table 2, but is not limited to this.

In another embodiment, the carbazole-substituted triazine compound is particularly preferably the compound (2-8).

In a specific embodiment, the carbazole-substituted triazine compound having the structure of formula (I), when m is 1 and n is 2, Z ₁ is hydrogen, and the compound of formula (I) is For compound (3-1):

In a specific aspect, when m is 2 and n is 0, the carbazole substituted triazine compound having the structure of formula (I), Z ₁ is hydrogen, and is represented by formula (III) or formula ( IV) Structural representation:

In a specific embodiment, when m is 2 and n is 0, the carbazole substituted triazine compound having the structure of formula (I), L is a phenyl group or a substituted pyrimidinyl group.

In another embodiment, the preferred embodiment of the carbazole-substituted triazine compound having the structure of formula (I) when m is 2 and n is 0, and Z ₁ is hydrogen is selected from the table 3 compounds, but not limited thereto.

In another embodiment, the carbazole-substituted triazine compound is particularly preferably the compound (4-1).

The carbazole-substituted triazine compound having the structure of formula (I), because a plurality of carbazole groups belong to a rigid structure, provides the carbazole-substituted triazine compound with good thermal stability, and by having The triazine group capable of pulling electrons combined with the carbazole group capable of pushing electrons, so that its triplet energy (E _T ) is between 2.61 and 2.72 eV, and the band gap (E _g ) is between 3.11 and 3.26 eV. It can effectively widen the energy band gap and solve the above-mentioned problems of the prior art.

The carbazole-substituted triazine compound of the present invention has a glass transition temperature between 89 and 191 ° C and can withstand a high temperature environment for a long period of time in an automobile. Therefore, it is suitable for an organic electroluminescent element of a display for an automobile.

The invention further provides an organic electro-optic light-emitting element, comprising: a cathode; an anode; and an organic layer interposed between the cathode and the anode, and the organic layer comprises the carbazole-substituted triazine compound of the present invention.

The organic layer of the organic electroluminescent device of the present invention may be at least A light-emitting layer, and in addition to the organic layer, the organic electro-optical light-emitting element may include a group selected from the group consisting of an electron transport layer, an electron injection layer, a light-emitting layer, a hole blocking layer, and an electron blocking layer, which are different from the organic layer At least one layer of the group. In one embodiment, the light-emitting layer includes a red phosphorescent guest material and a host material, and the host material corresponding to the guest material is a carbazole-substituted triazine compound of the present invention.

In a specific embodiment, the organic layer including the aforementioned carbazole-substituted triazine compound is preferably a light-emitting layer, and the thickness thereof is 20 nm to 30 nm.

In a specific embodiment, based on the total weight of the light-emitting layer, the content of the guest material is 2% to 8% by weight.

The structure of the organic electroluminescent device of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view of a specific embodiment of an organic electroluminescent device according to the present invention. The organic electroluminescent device 100 includes a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a cathode 180. The organic electroluminescent device 100 can be fabricated by sequentially depositing the above layers.

FIG. 2 is a schematic cross-sectional view of another embodiment of the organic electro-optical light-emitting device of the present invention. The organic electroluminescent device 200 includes a substrate 210, an anode 220, a hole injection layer 230, a hole transport layer 240, an exciton blocking layer 245, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270, and a cathode 280. The difference in FIG. 1 is that the exciton blocking layer 245 is disposed between the hole transport layer 240 and the light emitting layer 250.

FIG. 3 is a schematic cross-sectional view of another embodiment of the organic electro-optical light-emitting device of the present invention. The organic electroluminescent device 300 includes a substrate 310, an anode 320, a hole injection layer 330, a hole transport layer 340, a light emitting layer 350, an exciton blocking layer 355, an electron transport layer 360, an electron injection layer 370, and a cathode 380. The difference in FIG. 1 is that the exciton blocking layer 355 is disposed between the light emitting layer and the electron transporting layer 360.

The organic electroluminescent element can be manufactured according to the reverse structure of the elements shown in FIGS. 1 to 3. In these inverted structures, one or more layers can be added or subtracted as required.

The materials of the hole injection layer, the hole transport layer, the exciton blocking layer, the electron blocking layer, and the electron injection layer can be selected from conventional materials. For example, the electron transport material forming the electron transport layer is different from the material of the light emitting layer. Moreover, it has electron-transporting properties, thereby promoting the migration of electrons in the electron-transporting layer, and preventing the accumulation of carriers caused by the dissociation energy difference between the light-emitting layer and the electron-transporting layer.

In addition, U.S. Patent No. 5,844,363 discloses a flexible transparent substrate incorporating an anode, the entire contents of which are incorporated herein by reference. As exemplified by US Patent No. 20030230980, the p-type doped hole transport layer is doped with F ₄ -TCNQ in m-MTDATA with a molar ratio of 50: 1. The entire content is cited in the present invention. As exemplified by US Patent No. 20030230980, the n-type doped electron transporting layer is doped with BPhen at a molar ratio of 1: 1 to BPhen, and the entire content is cited in the present invention. As shown in US Patent Nos. 5703436 and 5707745, the entire contents of the cathode are cited in the present invention. The cathode has a thin metal layer, such as: magnesium / silver (Mg: Ag), and a transparent conductive coating that covers the thin metal layer by sputtering deposition. Layer (ITO Layer). The application and principle of each barrier layer disclosed in US Pat. Nos. 6,097,147 and 20030230980, the entire contents of which are cited in the present invention. The entire contents of the injection layer illustrated in US Patent No. 20040174116 and the protective layer described in the same case are cited in the present invention.

Structures and materials not specifically described can also be used in the present invention, as disclosed in US Patent No. 5,247,190, including organic electro-luminescent elements including polymer materials (PLEDs), the entire contents of which are incorporated herein by reference. Furthermore, for an organic electroluminescent device having a single organic layer or an organic electroluminescent device formed by stacking as disclosed in US Patent No. 5,707,745, the entire contents of which are incorporated herein by reference.

Unless specifically defined, any layer in different embodiments may be deposited using any suitable method. In terms of organic layers, the preferred methods include the thermal evaporation method and the printing method disclosed in US Patent Nos. 6013982 and 6087196, the entire contents of which are cited in the present invention; organic vapor deposition disclosed in US Patent No. 6337102 Organic vapor phase deposition (OVPD), the entire contents of which are cited in the present invention; organic vapor jet printing (OVJP) disclosed in US Patent No. 10/233470, the entire content of which is Cited by the present invention. Other suitable methods include spin coating and solution-based processes. The solution-based process is preferably performed in a nitrogen or inert gas environment. For other layers, a preferred method includes thermal evaporation. The preferred patterning method includes a process of mask deposition and re-cold welding as disclosed in U.S. Patent Nos. 6294398 and 6468819, and a process of integrating deposition or patterning by spray printing or organic vapor phase printing. Ming quoted. Of course, other methods can also be used. The materials used for deposition can be adjusted to suit the particular deposition method.

The carbazole-substituted triazine compound having the structure of formula (I) of the present invention can be made into an amorphous thin film applied to an organic electroluminescent device by vacuum deposition or spin coating. When the compound is used in the above-mentioned organic layer, it exhibits high device efficiency and good thermal stability.

The organic electro-optical light-emitting element of the present invention can be applied to a single element, and its structure is an array configuration or an element provided with yin and yang poles in the array X-Y coordinates. Compared with conventional devices, the present invention can significantly improve the performance and driving stability of organic electro-optical light-emitting devices. In addition, combined with the red light dopant in the light-emitting layer, the organic electroluminescent device of the present invention can achieve better performance and can emit white light when applied to a full-color or colorful display panel.

In the following, many properties and effects of the present invention are described in detail through examples. These detailed embodiments are only used to illustrate the nature of the present invention, and the present invention is limited to those exemplified by the specific embodiments.

Synthesis Example 1: Synthesis of Compound 1-1

N-phenyl-3-carbazole boronic acid (10.0 g, 34.8 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (18.7 g, 70.0 mmol) , Tetrakis (triphenylphosphine) palladium (2.0 g, 1.74 mmol) and tetrahydrofuran (250 ml) in that order Add 500 ml double-necked round bottom reaction flask, then add 50 ml of 2M potassium carbonate aqueous solution and fill the reaction system with nitrogen. Heat the system to reflux with an oil bath. After 16 hours of reaction, cool down the system and filter the suspension. It was washed with tetrahydrofuran (300 ml) in batches, the aqueous layer in the filtrate was removed, and the organic layer was washed with saturated brine, and the solvent was removed using a cycloconcentrator after removing water with anhydrous magnesium sulfate. Heavy tetrahydrofuran dissolves the crude product and recrystallizes by adding dropwise to 15 times the weight of the crude product in hexane to obtain compound 1-1 (12.0 g, 72%) as a off-white solid.

¹ H NMR (CDCl ₃ , 400MHz): δ 7.32 (dt, J = 6.0, 0.8Hz, 1H), 7.39-7.53 (m, 4H), 7.58-7.66 (m, 10H), 8.35 (d, J = 6.4 Hz, 1H), 8.82 (td, J = 8.0, 1.6Hz, 4H), 8.86 (dd, J = 6.8, 1.2Hz, 1H), 9.57 (d, J = 1.2Hz, 1H)

Synthesis Example 2: Synthesis of Compound 2-1

3- (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -carbazole (20.0 g, 71.1 mmol), 2-chloro -4,6-diphenyl-1,3,5-triazine (17.3 g, 64.7 mmol), tetrakis (triphenylphosphine) palladium (3.7 g, 3.23 mmol) and tetrahydrofuran (300 ml) A 1-liter double-necked round-bottomed reaction bottle was sequentially added, and then 100 ml of a 2M potassium carbonate aqueous solution was added and the reaction system was filled with nitrogen. The system was heated to reflux with an oil bath. After 16 hours of reaction, the system was cooled and filtered to suspend It was filtered off, and then tetrahydrofuran (300 ml) Rinse in batches, remove the aqueous layer from the filtrate and wash the organic layer with saturated brine, and then remove the solvent with anhydrous magnesium sulfate using a cycloconcentrator to remove the solvent. Dissolve the crude product with tetrahydrofuran equal to the crude product, and drip. Add 15 times the weight of the crude product and recrystallize to obtain compound 2-1-1a (13.7 g, 53%) as a off-white solid.

Carbazole (20.0 g, 119.6 mmol), 1-bromo-4-iodobenzene (38.0 g, 134.3 mmol), cuprous (I) chloride (2.37 g, 23.9 mmol), dimethyl 500 ml of a double-necked round bottom reaction was sequentially added to the sulfoximine (250 ml), potassium carbonate (33.1 g, 239.2 mmol) and 1,2-diaminocyclohexane (6.8 g, 59.8 mmol). Bottle, and fill the reaction system with nitrogen, heat the system to 110 ° C with an oil bath, cool the system after 16 hours and pour the reactants into 300 ml of water and stir, and then extract with ethyl acetate. It was washed with saturated brine, then removed with magnesium sulfate and filtered. The resulting filtrate was removed by a cycloconcentrator, and then silica gel column chromatography was used with hexane as the extraction system. A light brown solid was obtained as compound 2-. 1-b (15.7 g, 41%).

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 2-1-2 (4.04 g, 12.55 mmol), palladium acetate (0.06 g, 0.25 mmol), toluene (150 ml) 2. Sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-necked round bottom reaction flask, and the reaction system was filled with nitrogen. The system was heated to reflux with an oil bath. After 16 hours of reaction, the system was cooled down and stirred with 150 ml of ethyl acetate. The reaction was filtered, washed with ethyl acetate (300 ml) in batches, and the solid was dissolved in tetrahydrofuran. After filtration, the obtained filtrate was removed by a cycloconcentrator, and silica gel column chromatography was used with ethyl acetate and hexane as an elution system to obtain compound 2-1 (6.13 g, 76%) as an off-white solid.

¹ H NMR (CDCl ₃ , 400MHz): δ 7.36 (td, J = 7.6, 0.8Hz, 2H), 7.43-7.68 (m, 14H), 7.89 (s, 4H), 8.20 (d, J = 8.0Hz, 2H), 8.42 (d, J = 7.6Hz, 1H), 8.83-8.87 (m, 4H), 8.96 (dd, J = 8.0, 2.0Hz, 1H), 9.63 (d, J = 1.2Hz, 1H)

Synthesis Example 3: Synthesis of Compound 2-3

Carbazole (20.0 g, 119.6 mmol), 1-bromo-3-iodobenzene (38.0 g, 134.3 mmol), cuprous (I) chloride (2.37 g, 23.9 mmol), dimethyl 500 ml of a double-necked round bottom reaction was sequentially added to the sulfoximine (250 ml), potassium carbonate (33.1 g, 239.2 mmol) and 1,2-diaminocyclohexane (6.8 g, 59.8 mmol). Bottle, and fill the reaction system with nitrogen, heat the system to 110 ° C with an oil bath, cool the system after 16 hours and pour the reactants into 300 ml of water and stir, and then extract with ethyl acetate. It was washed with saturated brine, then removed with magnesium sulfate and filtered. The resulting filtrate was removed by a cycloconcentrator, and then silica gel column chromatography was used with hexane as the extraction system. A light brown solid was obtained as compound 2-. 3-b (17.61 g, 46%).

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 2-2-3b (4.04 g, 12.55 mmol), palladium acetate (0.06 g, 0.25 mmol) Mol), xylene (150 mL), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to 250 mL of a double-necked round bottom reaction Bottle, and fill the reaction system with nitrogen, heat the system to reflux with an oil bath, cool the system after 16 hours of reaction and add 150 ml of ethyl acetate to stir, then filter the reaction, and divide with ethyl acetate (300 ml) After batch washing, the solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed by a cycloconcentrator, and silica gel column chromatography was used with ethyl acetate and hexane as the extraction system. A white-like solid was obtained as compound 2-. 3 (5.00 g, 62%).

¹ H NMR (CDCl ₃ , 400MHz): δ 7.32 (t, J = 6.4Hz, 2H), 7.41 (t, J = 6.4Hz, 1H), 7.45-7.50 (m, 3H), 7.55-7.65 (m, 10H), 7.73 (dt, J = 8.0, 1.6Hz, 2H), 7.86 (t, J = 1.6Hz, 2H), 7.89 (t, J = 6.4Hz, 1H), 8.17 (d, J = 6.0Hz, 2H), 8.37 (d, J = 6.0Hz, 1H), 8.82 (td, J = 6.0, 1.6Hz, 4H), 8.91 (dd, J = 7.2, 1.2Hz, 1H), 9.57 (d, J = 1.2 Hz, 1H)

Synthesis Example 4: Synthesis of Compound 2-4

Compound 2-1-1a (7.50 g, 18.82 mmol), 1,4-diiodobenzene (3.10 g, 9.41 mmol), palladium acetate (0.08 g, 0.38 mmol), Xylene (150 ml), sodium tert-butoxide (3.60 g, 37.46 mmol) and tri-tert-butylphosphine (0.30 g, 1.51 mmol) were sequentially added to a 250 ml double-necked round bottom reaction flask, and Nitrogen was used to fill the reaction system. The system was heated to reflux with an oil bath. After 16 hours of reaction, the system was cooled and stirred with 150 ml of ethyl acetate. The reaction was then filtered and rinsed with tetrahydrofuran (300 ml) in batches. Purification by Tetrahydrofuran and Tetrahydrofuran, Compound 2-4 (6.13 g, 74%) was obtained as a off-white solid.

MS m / z: [M] + C ₆₀ H ₃₈ N8 The calculated value is 870.3, and the actual value is 870.3.

Synthesis Example 5: Synthesis of Compound 2-5

5,7-Dihydro-7,7-dimethyl-indeno [2,1-b] carbazole (33.9 g, 119.6 mmol), 1-bromo-4-iodobenzene (38.0 g, 134.3 Mmol), cuprous (I) iodide (4.55 g, 23.9 mmol), dimethylsulfine (250 ml), potassium carbonate (33.1 g, 239.2 mmol) and 1,2-diamine Cyclohexane (6.8 g, 59.8 mmol) was sequentially added to a 500 ml double-necked round-bottomed reaction flask, and the reaction system was filled with nitrogen. The system was heated to 110 ° C in an oil bath, and the system was cooled after 16 hours of reaction. The reaction was poured into 300 ml of water and stirred. After extraction with ethyl acetate, the extract was washed with saturated brine, and then water was removed with magnesium sulfate and filtered. The resulting filtrate was removed by a cycloconcentrator and the solvent was removed. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, compound 2-5-b (41.9 g, 80%) was obtained as a light brown solid.

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 2-5-b (5.50 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-neck round bottom reaction flask, and Fill the reaction system with nitrogen, heat the system to reflux with an oil bath, cool down the system after 16 hours of reaction and add 150 ml of ethyl acetate to stir, then filter the reaction, and rinse with ethyl acetate (300 ml) in batches The solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed by a cycloconcentrator, and silica gel column chromatography was used with ethyl acetate and hexane as the extraction system. A white-like solid was obtained as compound 2-5 (7.12 G, 75%).

¹ H NMR (CDCl ₃ , 400MHz): δ 1.58 (s, 6H), 7.30-7.66 (m, 10H), 7.73 (d, J = 6.8Hz, 1H), 7.89 (d, J = 6.0Hz 1H), 7.92 (s, 4H), 8.25 (d, J = 6.4Hz, 1H), 8.42 (d, J = 6.4Hz, 1H), 8.49 (s, 1H), 8.86 (dt, J = 6.8, 1.2Hz, 4H ), 8.98 (dd, J = 6.8, 1.6Hz, 1H), 9.64 (dd, J = 0.8Hz 1H)

Synthesis Example 6: Synthesis of Compound 2-6

9,10-dihydro-9,9-dimethylacridine (25.0 g, 119.6 mmol), 1-bromo-4-iodobenzene (38.0 g, 134.3 mmol), cuprous chloride ( I) (2.37 g, 23.9 mmol), dimethyl sulfene (250 ml), potassium carbonate (33.1 g, 239.2 mmol) and 1,2-diaminocyclohexane (6.8 g, 59.8 mmol) Mol) Sequentially added a 500 ml double-necked round bottom reaction flask, and filled the reaction system with nitrogen. The system was heated to 110 ° C with an oil bath. After 16 hours of reaction, the system was cooled and the reaction was poured into 300 ml of water and stirred. Then, after extracting with ethyl acetate, the extract was washed with saturated brine, and then water was removed with magnesium sulfate and filtered. The resulting filtrate was removed by a cycloconcentrator, and then silica gel column chromatography was used with hexane as the solvent. By stripping the system, compound 2-6-b (9.15 g, 21%) was obtained as a light brown solid.

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 2-6-b (4.57 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol), xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol), and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-necked circle Bottom reaction flask and fill the reaction system with nitrogen. Heat the system to reflux with an oil bath. After 16 hours of reaction, cool down the system and add 150 ml of ethyl acetate to stir. Then filter the reaction, and then use ethyl acetate (300 ml ) After washing in batches, the solid was dissolved in tetrahydrofuran and then filtered. The resulting filtrate was removed by a cycloconcentrator. The silica gel column chromatography was used with ethyl acetate and hexane as the extraction system. A white-like solid was obtained as the compound. 2-6 (5.82 g, 68%).

¹ H NMR (CDCl ₃ , 400MHz): δ 1.75 (s, 6H), 6.46 (m, J = 8.4Hz, 2H), 7.01 (t, J = 7.6Hz2H), 7.10 (t, J = 7.6Hz, 2H ), 7.44-7.70 (m, 14H), 7.92 (d, J = 8.0Hz, 2H), 8.41 (d, J = 8.0Hz, 1H), 8.84 (d, J = 6.4Hz, 4H), 8.96 (d , J = 8.0Hz, 1H), 9.62 (s, 1H)

Synthesis Example 7: Synthesis of compound 2-8

4- (N- (naphthalen-1-yl) -N-aniline) phenylboronic acid (30.0 g, 44.2 mmol), 4-chlorobromobenzene (9.3 g, 48.7 mmol), tetrakis (triphenyl) Phosphonium) palladium (1.0 g, 0.9 mmol) and tetrahydrofuran (400 ml) were sequentially added to a 1 liter double-necked round-bottomed reaction flask, followed by 150 ml of a 2 M potassium carbonate aqueous solution and filling the reaction system with nitrogen. Heat to reflux with an oil bath. After 16 hours of reaction, the system was cooled and filtered. The suspension was filtered off and the filtrate was extracted with ethyl acetate. The aqueous layer was removed and the organic layer was washed with saturated brine. After removing water with anhydrous magnesium sulfate, the solvent was removed using a cycloconcentrator. Finally, silica gel column chromatography and a hexane extraction system were used to obtain compound 2-8-b (17.7 g, 97%) as a white to light brown solid.

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 2-8-b (5.64 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-neck round bottom reaction flask, and Fill the reaction system with nitrogen, heat the system to reflux with an oil bath, cool the system after 60 hours of reaction and add 150 ml of ethyl acetate to stir, then filter the reaction, and rinse with ethyl acetate (300 ml) in batches The solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed by a cycloconcentrator, and silica gel column chromatography was used with ethyl acetate and hexane as the extraction system. A white-like solid was obtained as compound 2-8 (5.40 G, 56%).

¹ H NMR (CDCl ₃ , 400MHz): δ 7.01 (t, J = 6.4Hz, 1H), 7.16 (t, J = 6.8Hz, 4H), 7.25-7.83 (m, 19H), 7.81-7.83 (m, 3H), 7.92 (d, J = 6.4Hz, 1H), 8.00 (d, J = 6.4Hz, 1H), 8.37 (d, J = 6.4Hz, 1H), 8.84 (dd, J = 6.0, 0.8Hz, 4H), 8.89 (dd, J = 6.8, 0.8Hz, 1H), 9.59 (dd, J = 0.4Hz 1H)

Synthesis Example 8: Synthesis of Compound 3-1

Add carbazole (15.00 g, 89.71 mmol), dimethylacetamide (50 ml), and cesium carbonate (43.84 g, 134.55 mmol) to a 250 ml double-necked round-bottomed reaction bottle in this order. Fill the reaction system with nitrogen, heat the system to 70 ° C with an oil bath and stir for 30 minutes, then add 3,5-difluorobromobenzene (8.66 g, 44.85 mmol) and another 40 ml of dimethylacetamide, After 16 hours of reaction, the system was cooled down and the reaction was diluted with 100 ml of tetrahydrofuran and stirred at room temperature for 1 hour, then poured into water and extracted with ethyl acetate. The collected organic layer was washed with eye water when saturated, and then concentrated Chromatography with a silica gel tube gave compound 3-1-3b (13.1 g, 60%) as a white solid.

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 3-1-b (6.12 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol), xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol) Mol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-necked round bottom reaction flask, and the reaction system was filled with nitrogen. The system was heated to reflux with an oil bath. After an hour, the system was cooled and 150 ml of ethyl acetate was added and stirred. The reaction was filtered and washed with ethyl acetate (300 ml) in batches. The solid was dissolved in tetrahydrofuran and then filtered. The resulting filtrate was removed by a cycloconcentrator. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, compounds 2-8 (7.98 g, 79%) can be obtained as off-white solids.

¹ H NMR (CDCl ₃ , 400MHz): δ 7.36-7.73 (m, 19H), 7.77 (d, J = 7.2Hz 1H), 7.98 (s, 4H), 8.03 (s, 1H), 8.19 (d, J = 6.4Hz, 4H), 8.37 (d, J = 6.0Hz, 1H), 8.80 (dd, J = 7.2, 2.0Hz, 4H), 8.94 (d, J = 7.2Hz, 1H), 9.57 (s, 1H )

Synthesis Example 9: Synthesis of Compound 4-1

Compound 2-1-1a (5.00 g, 12.55 mmol), 3-bromo-N-phenyl-carbazole (4.04 g, 12.55 mmol), palladium acetate (0.06 g, 0.25 mmol), Toluene (100 mL), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 mL double-necked round-bottomed reaction flask, followed by nitrogen Fill the reaction system with oil The bath was heated to reflux. After 16 hours of reaction, the system was cooled down and stirred with 150 ml of ethyl acetate. The reaction was filtered and washed with ethyl acetate (300 ml) in portions. The solid was dissolved in tetrahydrofuran and filtered. The filtrate was removed by a cycloconcentrator, and tetrahydrofuran and hexane were used as recrystallization to obtain compound 4-1 (4.98 g, 62%) as an off-white solid.

¹ H NMR (CDCl ₃ , 400MHz): δ 7.42-7.90 (m, 21H), 8.15 (d, J = 6.8Hz, 1H), 8.35 (d, J = 2.0Hz, 1H), 8.41 (d, J = 8.0Hz, 1H), 8.83-8.90 (m, 4H), 9.64 (d, J = 2.0, 1H)

Synthesis Example 10: Synthesis of Compound 4-3

Add 3-bromocarbazole (10.0 g, 40.6 mmol), dimethylacetamide (50 ml), and cesium carbonate (26.5 g, 81.3 mmol) to a 250 ml double-necked round bottom reaction bottle in this order. And filled the reaction system with nitrogen, heated the system to 70 ° C with an oil bath and stirred for 30 minutes, then added 2-chloro-4,6-diphenylpyrimidine (10.8 g, 40.6 mmol) and another 50 ml of Dimethylacetamide. After 16 hours of reaction, the system was cooled and the reaction was filtered and washed with 50 ml of dimethylacetamide and 100 ml of tetrahydrofuran. Then the solid in the white porcelain funnel was washed with plenty of water. Funnel The remaining solid was poured into 200 ml of tetrahydrofuran, heated to 65 ° C. and stirred for 30 minutes, and filtered while hot to obtain a white solid, which was compound 4-3-b (14.9 g, 68%).

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 4-3-b (5.98 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were sequentially added to a 250 ml double-neck round bottom reaction flask, and Fill the reaction system with nitrogen, heat the system to reflux with an oil bath, and cool the system after 72 hours of reaction and add 150 ml of ethyl acetate to stir. Then filter the reaction and rinse with ethyl acetate (300 ml) in batches. The solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed by a cycloconcentrator, and tetrahydrofuran and hexane were used as recrystallization. Compound 4-1 (7.37 g, 74%) was obtained as a off-white solid.

¹ H NMR (CDCl ₃ , 400MHz): δ 7.39-7.52 (m, 4H), 7.58-7.64 (m, 15H), 7.75 (dd, J = 8.8, 2.4Hz, 1H), 8.04 (s, 1H), 8.11 (d, J = 7.6Hz, 1H), 8.31-8.35 (m, 6H), 8.40 (d, J = 7.6Hz, 1H), 8.85 (td, J = 7.2, 2Hz, 2H), 8.90 (dd, J = 8.4, 1.6Hz, 1H), 9.07 (d, J = 8.4Hz, 1H), 9.25 (d, J = 8.4Hz, 1H), 9.64 (s, 1H)

Synthesis Example 11: Synthesis of compound 4-4

Add 2-bromocarbazole (10.0 g, 40.6 mmol), dimethylacetamide (50 ml), and cesium carbonate (26.5 g, 81.3 mmol) to a 250 ml double-necked round bottom reaction bottle in this order. And filled the reaction system with nitrogen, heated the system to 70 ° C with an oil bath and stirred for 30 minutes, then added 2-chloro-4,6-diphenylpyrimidine (10.8 g, 40.6 mmol) and another 50 ml of Dimethylacetamide. After 16 hours of reaction, the system was cooled and the reaction was filtered and washed with 50 ml of dimethylacetamide and 100 ml of tetrahydrofuran. Then the solid in the white porcelain funnel was washed with plenty of water. Funnel The remaining solid was poured into 200 ml of tetrahydrofuran, heated to 65 ° C. and stirred for 30 minutes, and filtered while hot to obtain a white solid, which was compound 4-4-b (14.9 g, 97%).

Compound 2-1-1a (5.00 g, 12.55 mmol), compound 4-3-b (5.98 g, 12.55 mmol), bis (dibenzylacetyl) palladium (0.14 g, 0.25 mmol) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 mmol) and tri-tert-butylphosphine (0.25 g, 12.6 mmol) were added sequentially A 250 ml double-necked round-bottomed reaction flask was filled, and the reaction system was filled with nitrogen. The system was heated to reflux with an oil bath. After 72 hours of reaction, the system was cooled and 150 ml of ethyl acetate was added to stir. Then the reaction was filtered, and After washing with ethyl acetate (300 ml) in batches, the solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed by a cycloconcentrator and the solvent was recrystallized using tetrahydrofuran and hexane to obtain a off-white solid, which is compound 4- 1 (8.97 g, 90%).

MS m / z: [M] + C ₅₅ H ₃₅ N _{7 The} calculated value is 793.3, and the actual value is 793.3.

The physical property values of the above materials are shown in Table 4. The measurement method of each physical property value is shown below.

(1) Thermal cracking temperature (T _d )

The thermogravimetric analyzer (Perkin Elmer, TGA 8000) was used for measurement. The thermal cracking properties of the prepared compounds were measured under a normal pressure and nitrogen atmosphere at a program temperature increase rate of 20 ° C / min. The temperature at which the weight is reduced to 95% of the initial weight is the thermal cracking temperature (T _d ).

(2) Glass transition temperature (T _g )

A differential scanning thermal analyzer (DSC; Perkin Elmer, DSC 8000) was used to measure the prepared compound at a program temperature increase rate of 20 ° C / minute.

(3) Energy level of the highest occupied molecular orbital (HOMO)

In addition, the compound is made into a thin film state, and its ionization potential value is measured with a photoelectron spectrophotometer (Riken Keiki, Surface Analyzer AC-II) in the atmosphere, and the value is further converted into a HOMO energy level value.

(4) Energy band gap value (E _g ) and energy level value of the lowest unoccupied molecular orbital (LUMO)

The thin film of the above compound was measured with a UV / VIS spectrophotometer (Perkin Elmer, Lambda 20) for the boundary value of its absorption wavelength, and the value was converted into an energy band gap value (Eg), so that the energy band gap value and HOMO energy The numerical values of the order are added to obtain the LUMO energy order.

(5) Triplet energy value (E _T )

Fluorescence spectrometer (Perkin Elmer, LS 55) was used to measure the luminescence spectrum at a temperature of 77K, and E _T was obtained by calculation.

(6) Wavelength of emitted light (PL)

A fluorescence excitation spectrometer (Perkin Elmer, LS 55) was used to measure the fluorescence spectrum of each synthesis example in the state of a tetrahydrofuran solution. The measurement conditions were: a concentration of 10 ^-5 M and a measurement range of 300 to 800 nm wavelength.

Example 1: Manufacture of organic electro-optical light-emitting element

Before the substrate is loaded into the evaporation system, the substrate is cleaned with a solvent and ultraviolet ozone for degreasing. After that, the substrate is transferred to a vacuum deposition chamber, and all layers are deposited on top of the substrate. The layers shown in Figure 2 are sequentially deposited by a heated evaporation boat at a vacuum of about 10 ^-6 Torr: a) hole injection layer, 20 nanometers thick, containing 9% p HTM-type electrically conductive dopants, wherein the p-type electrically conductive dopants were purchased from Shanghai Hanfeng Chemical Co., Ltd. and the HTM was purchased from Merck & Co., Inc .; b) hole transport layer, Thickness 140 nm, HTM; c) exciton blocking layer, thickness 10 nm, HT (prepared by Yu Rai Optoelectronics); d) light emitting layer, 30 nm thick, containing 4% volume ratio PER Preparation) of Compound 1-1; e) Electron transport layer, 30 nm thick, containing compound ET-1 (prepared by Yu Lei Optoelectronics) and doped lithium quinoline (Liq, produced by Yu Lei Optoelectronics); f) electron injection Layer, with a thickness of 0.5 nm, LiF; and g) a cathode, with a thickness of about 150 nm, Al.

The element structure can be expressed as: ITO / HTM: 9% p-type electrically conductive dopant (20 nm) / HTM (140 nm) / HT (10 nm) / Compound 1-1: 4% PER (30 nm M) / Chem. ET-1: Liq (30 nm) / LiF (0.5 nm) / Al (150 nm).

After the above layers are formed by deposition, the element is transferred from the deposition chamber to a drying box, and then encapsulated with a UV curable epoxy resin and a glass cover plate containing a hygroscopic agent. The organic electroluminescent device has a light emitting area of 9 mm 2.

Embodiments 2 to 8: Manufacturing of Organic Electrically Excited Optical Elements

Except that the compounds 1-1 in the light-emitting layer in Example 1 were replaced with compounds Objects 2-1, 2-3, 2-6, 2-8, 3-1, 4-1, and 4-3, Example 2, Example 3, Example 4, Example 5, Example 6, Implementation Example 7 and Example 8 have the layer structure of Example 1, and the doping volume of the guest material PER is changed as shown in Table 5.

Comparative Examples 1 to 2: Production of Organic Electro-Optic Excitation Light Element

The organic electroluminescent element was structured to have a layer structure similar to that of Example 1, except that the compound 1-1 of the light-emitting layer in Example 1 was replaced with the compounds EPH-1 and EPH-2 / HT (weight ratio 1: 1) ), EPH-1 is the material in our company's patent number US 8,592,055 B2, which is prepared by Yu Lei Optoelectronics, EPH-2 is the material in Nippon Steel & Sumikin Chemical Patent No. US 8,993,129 B2, which is prepared by Yu Lei Optoelectronics. Comparative Example 2 has the layer structure of Example 1, and the doping volume of the guest material PER is changed as shown in Table 5.

The electro-excitation light properties of the above-mentioned organic electro-excitation light elements are all Measured at room temperature with a constant current source (KEITHLEY 2400 Source Meter, made by Keithley Instruments, Inc., Cleveland, Ohio) and a photometer (PHOTO RESEARCH SpectraScan PR 650, made by Photo Research, Inc., Chatsworth, Calif.) The luminous properties are shown in Table 5 for the driving voltage and luminous efficiency.

As described above, within an acceptable driving voltage variation range, it can be seen that the organic electroluminescent device including the carbazole-substituted triazine compound having the formula (I) structure of the present invention exhibits good heat resistance and significantly improves its luminous efficiency. Therefore, the organic electroluminescence light element of the present invention is suitable for application fields such as automotive displays, and has extremely high technical value.

The above-mentioned embodiments are merely illustrative and not intended to limit the present invention. Anyone skilled in the art can modify and change the above embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the rights of the present invention is defined by the scope of the patent application attached to the present invention, as long as it does not affect the effect and implementation purpose of the present invention, it should be covered in this disclosed technical content.

Claims (15)

A carbazole-substituted triazine compound having the structure of formula (I): Among them, Ar _{1 is} each the same or different, and each Ar ₁ independently represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _6-30 aryl, and substituted or unsubstituted A C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; m represents an integer of 1 or 2; n represents an integer of 0 to 2; wherein n is 0 , L represents a substituted or unsubstituted C _5-12 aryl group, and a substituted or unsubstituted C _3-40 containing at least one heteroatom selected from the group consisting of N, O, and S Heteroaryl; and when n is 1 or 2, L represents a substituted or unsubstituted C _5-12 arylene group, and the substituted or unsubstituted group contains a member selected from the group consisting of N, O, and S At least one hetero atom of C _3-40 heteroaryl; Z ₁ represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _5-12 aryl, and substituted or unsubstituted A substituted C _3-40 heteroaryl group containing at least one heteroatom selected from the group consisting of N, O, and S; and X ₁ is a structure of formula (I-1) or formula (I-2) : Among them, G represents a single bond, C atom, O atom, or S atom; B represents hydrogen, substituted or unsubstituted C containing at least one heteroatom selected from the group consisting of N, O, and S _3-10 heteroaryl or substituted or unsubstituted _C6-12 bicyclic ring fused with a compound of formula (I-1); R ₁ each independently represents hydrogen or C _1-4 alkyl; R ₂ and R ₃ are Are the same or different, and each of R ₂ and R ₃ independently represents hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from the group consisting of N, O, and S A C _3-40 heteroaryl group of at least one heteroatom in the group formed; and f represents an integer of 0 to 2. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 1 of the scope of the patent application is represented by the structure of formula (II): The carbazole-substituted triazine compound having the formula (I) structure as described in item 1 of the scope of the patent application, wherein X ₁ is selected from one of the following groups: The carbazole-substituted triazine compound having the formula (I) structure as described in item 1 of the scope of the patent application, wherein, when n is 0, L is selected from substituted or unsubstituted phenyl and biphenyl Or pyrimidinyl; when n is 1 or 2, L is selected from substituted or unsubstituted phenyl, biphenyl, or pyrimidinyl. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 1 of the scope of the patent application, wherein Z ₁ is a substituted triazine group. The carbazole-substituted triazine compound having the formula (I) structure as described in item 1 of the scope of the patent application, wherein when m is 1 and n is 0, L is phenyl. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 6 of the scope of the patent application, wherein the compound of formula (I) represents compound (1-2), The carbazole-substituted triazine compound having the formula (I) structure as described in item 1 of the scope of the patent application, wherein when m is 1 and n is 1, L is a phenylene group or a phenylene group. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 8 of the scope of application for a patent, wherein the compound of formula (I) represents the compound (2-8), The carbazole-substituted triazine compound having the structure of formula (I) as described in item 1 of the scope of the patent application, wherein when m is 2 and n is 0, the structure is of formula (III) or formula (IV) Means: The carbazole-substituted triazine compound having the structure of formula (I) as described in item 10 of the scope of the patent application, wherein L is a phenyl group or a substituted pyrimidinyl group. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 11 of the scope of the patent application, wherein the compound of formula (I) represents compound (4-1), An organic electro-optical light-emitting element includes: a cathode; an anode; and an organic layer interposed between the cathode and the anode, and the organic layer includes a structure having the formula (I) as described in item 1 of the scope of patent application. Carbazole-substituted triazine compounds. The organic electro-optical light-emitting device according to item 11 of the scope of application, wherein the organic layer is a light-emitting layer, and the thickness is 20 nm to 40 nm. The organic electroluminescent device according to item 11 of the scope of patent application, wherein the light-emitting layer comprises a guest material, and the content of the guest material is 2% to 8% by weight based on the total weight of the light-emitting layer. .