TWI706946B - 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

Triazine compound substituted by carbazole and its organic electroluminescent element

The present invention relates to a material for an organic electroluminescent device and an organic electroluminescent device using the material, and more particularly to a material that can improve the performance of the device and an organic electroluminescent device using the material.

Organic electroluminescent element (OLED) is regarded as the most potential flat display technology because of its light, thin, wide viewing angle, high contrast, low power consumption, high response speed, full color and flexibility. , In order to meet the application of the organic electroluminescence element, special emphasis is placed on the development of its novel organic materials.

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 migrate to opposite charged electrodes. When electrons and holes are confined to the same molecule, an "exciton" is formed. This exciton is a localized electron-hole pair with an excited energy state. The exciton relaxes and emits light through the luminescence mechanism. .

The multi-layer film structure of OLED is to provide good device efficiency and service life. The key considerations include the stability of the interface between the electrodes and the organic layer and the combination of commensurate organic layers. If a light-emitting layer material of a commensurate energy level is used, The holes and electrons can be effectively transferred to the light-emitting layer, so that the density of the electrons and holes in the light-emitting layer is balanced, and the luminous efficiency is increased. The literature has published the method of blending another guest material with the host material, which can also improve the performance of the device and adjust the chromaticity. Several OLED materials and device configurations are described in U.S. Patent Nos. 4,769,292, 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 the mobility of electrons and holes. However, the carbazole compounds easily cause the band gap to become smaller, making the performance of OLED devices difficult to meet the needs of actual display applications, especially for For automotive displays, the organic materials used in organic electroluminescent devices must have good thermal stability to maintain the luminous chromaticity and luminous efficiency requirements of the devices.

Therefore, there is an urgent need for an organic material with good heat resistance, which can significantly improve the performance of organic electroluminescent devices to meet the needs of diverse applications.

The purpose of the present invention is to provide a material for organic electroluminescent devices that can promote the balance of the electrons and holes in the light-emitting layer, improve the luminous efficiency and have good heat resistance.

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

其中，G係表示單鍵、C原子、O原子或S原子；B係表示氫、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-10雜芳基或與式(I-1)化合物稠合之經取代或未經取代之C_6-12雙環；R₁各獨立表示氫或C_1-4烷基；R₂、R₃係為相同或相異，且各R₂和R₃獨立表示氫、氰基、經取代或未經取代之C_6-12芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-40雜芳基；以及f表示0至2之整數。 Wherein, Ar ₁ are 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 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; wherein, n is 0 When, 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 a substituted or unsubstituted C _5-12 aryl group selected from the group consisting of N, O, and S At least one heteroatom in the C _3-40 heteroaryl group; 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 represents the structure of formula (I-1) or formula (I-2) :

Wherein, 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 of R ₂ and R ₃ independently represents hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group consisting of S; and f represents an integer from 0 to 2.

The present invention further provides an organic electroluminescent device, comprising: a cathode; an anode; and an organic layer, which is interposed between the cathode and the anode, and the organic layer includes the above-mentioned structure of formula (I) substituted by carbazole Triazine compounds.

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

100, 200, 300‧‧‧Organic electroluminescence element

110、210、310‧‧‧Substrate

120、220、320‧‧‧Anode

130, 230, 330‧‧‧hole injection layer

140, 240, 340‧‧‧hole transmission layer

150, 250, 350‧‧‧Emitting layer

160, 260, 360‧‧‧ electron transport layer

170, 270, 370‧‧‧Electron injection layer

180、280、380‧‧‧Cathode

245、355‧‧‧ exciton blocking layer

The embodiment of the present invention will be explained through exemplary reference to the drawings: Figure 1 is a schematic cross-sectional view of one embodiment of the organic electroluminescent device of the present invention; Figure 2 is another embodiment of the organic electroluminescent device of the present invention Example of a schematic cross-sectional view; and Figure 3 is another example of the organic electroluminescent device of the present invention Schematic cross-section.

The following is a specific embodiment to illustrate the implementation 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 based on different viewpoints and applications, without departing from the spirit of the present invention. In addition, all ranges and values herein are inclusive and combinable. Any value or point falling within the range described herein, for example, any integer can be used as the minimum or maximum value to derive the lower range and so on.

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

其中，G係表示單鍵、C原子、O原子或S原子；B係表示氫、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-10雜芳基或與式(I-1)化合物稠合之經取代或未經取代之C_6-12雙環；R₁各獨立表示氫或C_1-4烷基；R₂、R₃係為相同或相異，且各R₂和R₃獨立表示氫、氰基、經取代或未經取代之C_6-12芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-40雜芳基；以及f表示0至2之整數。 Wherein, Ar ₁ are 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 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; wherein, n is 0 When, 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 a substituted or unsubstituted C _5-12 aryl group selected from the group consisting of N, O, and S At least one heteroatom in the C _3-40 heteroaryl group; 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 represents the structure of formula (I-1) or formula (I-2) :

Wherein, 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 of R ₂ and R ₃ independently represents hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group consisting of S; and f represents an integer from 0 to 2.

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

其中，G係表示單鍵、C原子、O原子或S原子；B係表示氫、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-10雜芳基或與式(I-1)化合物稠合之經取代或未經取代之C_6-12雙環；R₁各獨立表示氫或C_1-4烷基；R₂、R₃係為相同或相異，且各R₂和R₃獨立表示氫、氰基、經取代或未經取代之C_6-12芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C_3-40雜芳基；以及f表示0至2之整數。 Wherein, Ar ₁ are 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 It 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 a substituted or unsubstituted C _5-12 arylene group, a substituted or unsubstituted containing at least one heteroatom selected from the group consisting of N, O, and S_的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 C _3-40 heteroaryl group of at least one heteroatom in the group consisting of, O, and S; and X ₁ represents the structure of formula (I-1) or formula (I-2):

Wherein, 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 of R ₂ and R ₃ independently represents hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group consisting of S; and f represents an integer from 0 to 2.

In the text, the expression "substituted" in "substituted or unsubstituted" means that a hydrogen atom in a certain functional group is replaced by another atom or group (ie, a substituent). The substituents are each independently selected from at least one of the following groups: deuterium, halogen, C _1-30 alkyl, C _1-30 alkoxy, C _6-30 aryl, C _{5- 30} heteroaryl, C _5-30 heteroaryl substituted by C _6-30 aryl, benzimidazolyl, C _3-30 cycloalkyl, C _5-7 heterocycloalkyl, tri-C _1-30 alkane Base silyl group, tri-C _1-30 aryl silyl group, two C _1-30 alkyl group, C _6-30 aryl silyl group, C _1-30 alkyl group, two C _6-30 aryl silyl group, C _2-30 Alkenyl, C _2-30 alkynyl, cyano, two C _1-30 alkylamino, two C _6-30 aryl boron, two C _1-30 alkyl boron, C _1-30 alkyl, C _6-30 aryl, C _1-30 alkyl, C _1-30 alkyl, C _6-30 aryl, carboxy, nitro and hydroxyl.

In the text, "aryl" means an aryl group or (extended) aryl group. The aryl group refers to a monocyclic ring or a condensed polycyclic ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, triphenyl, Naphthyl, binaphthyl, phenyl naphthyl, naphthyl phenyl, stilbene, phenyl stilbene, benzo stilbene, dibenzo stilbene, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, Triphenylene, pyrenyl, fused tetraphenyl, perylenyl, quinyl, naphthonaphthyl, allenyl and so on.

唑基、

唑基、

二唑基、三

基、四

基、三唑基、四唑基、呋呫基、吡啶基、吡

基、嘧啶基、嗒

基等，或為與至少一個苯環縮合的稠合環，如苯并呋喃基、苯并噻吩基、異苯并呋喃基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、苯并噻唑基、苯并異噻唑基、苯并異

唑基、喹啉基、異喹啉基、噌啉基、喹唑啉基、喹

啉基、咔唑基、啡

唑基、啡啶基、苯并二

呃基、二氫吖啶基等。 In the text, "heteroaryl" means heteroaryl or (extended) heteroaryl, and the heteroaryl refers to a ring main chain atom containing at least one heteroatom selected from the group consisting of N, O, and S The aryl group can be a single ring system ring, such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, iso

Azole,

Azole,

Diazolyl, three

Base, four

Group, triazolyl, tetrazolyl, furyl, pyridyl, pyridine

Base, pyrimidinyl, ta

Group, etc., or a fused ring condensed with at least one benzene ring, such as benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, Benzothiazolyl, benzisothiazolyl, benziso

Azolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoline

Linyl, carbazolyl, phenanthrene

Azolyl, phenanthridinyl, benzodi

Er group, dihydroacridinyl group, etc.

In a specific embodiment, B represents a substituted C _6-12 bicyclic ring fused with the 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 structure of formula (I) is selected from one of the following groups:

In a specific embodiment, the carbazole-substituted triazine compound having the structure of formula (I), when n is 0, L is selected from substituted or unsubstituted phenyl, biphenyl or Pyrimidyl; when n is 1 or 2, L is selected from substituted or unsubstituted phenylene, biphenylene or pyrimidinyl.

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

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

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

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

In a specific embodiment, the carbazole-substituted triazine compound with the structure of formula (I) when m is 1 and n is 1, L is a divalent group and is selected from the group containing unsubstituted Phenyl, or unsubstituted biphenyl.

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

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

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

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

In a specific embodiment, when m is 2 and n is 0 in 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 carbazole-substituted triazine compound having the structure of formula (I), when m is 2 and n is 0, and Z ₁ is hydrogen, the preferred embodiment is selected from the table Compound 3, but not limited to this.

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

The carbazole-substituted triazine compound with the structure of formula (I), because multiple carbazole groups belong to a rigid structure, provides good thermal stability of the carbazole-substituted triazine compound, and by having The electron withdrawing ability of the triazine group is combined with the electron pushing ability of the carbazole group, so that the triplet energy (E _T ) is between 2.61 to 2.72 eV, and the energy band gap (E _g ) is between 3.11 to 3.26 eV , Can effectively enlarge 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 of between 89 and 191°C and can withstand a long-term high temperature environment inside a car, so it is suitable for organic electroluminescent elements of car displays.

The present invention further provides an organic electroluminescent device, comprising: a cathode; an anode; and an organic layer, which is interposed between the cathode and the anode, and the organic layer includes 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 electroluminescent element may include a different organic layer 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 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 the carbazole-substituted triazine compound of the present invention.

In a specific embodiment, the organic layer containing 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 in conjunction with the drawings.

Figure 1 is a schematic cross-sectional view of a specific embodiment of the organic electroluminescent device of 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-mentioned layers.

Figure 2 is a schematic cross-sectional view of another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent element 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, and a The difference in Figure 1 is that the exciton blocking layer 245 is disposed between the hole transport layer 240 and the light emitting layer 250.

Figure 3 is a schematic cross-sectional view of another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent element 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, and a The difference in Figure 1 is that the exciton blocking layer 355 is provided between the light emitting layer and the electron transport layer 360.

The organic electroluminescent device can be manufactured according to the reverse structure of the device shown in Figure 1 to Figure 3. One or more layers can be added or removed in these reversed structures as required.

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

In addition, US Patent No. 5,844,363 discloses a flexible transparent substrate combined with an anode, the entire content of which is cited in the present invention. As illustrated in US Patent No. 20030230980, the p-type doped hole transport layer is doped with F ₄ -TCNQ at a molar ratio of 50:1 to m-MTDATA, the entire contents of which are cited in the present invention. As exemplified in US Patent No. 20030230980, the n-type doped electron transport layer is doped with lithium in BPhen with a molar ratio of 1:1, and the entire content is cited in the present invention. The entire contents of the cathode as exemplified in US Patent Nos. 5703436 and 5707745 are cited in the present invention. The cathode has a thin metal layer, such as magnesium/silver (Mg: Ag), and a transparent conductive layer covered with the metal thin layer by sputtering deposition. Layer (ITO Layer). The application and principle of each barrier layer disclosed in US Patent Nos. 6097147 and 20030230980 are all cited in the present invention. The injection layer illustrated in US Patent No. 20040174116 and the protective layer illustrated in the same case are all cited in the present invention.

Structures and materials that are not specifically described can also be applied to the present invention. As disclosed in US Patent No. 5247190, organic electroluminescent devices including polymer materials (PLEDs), the entire contents of which are cited in the present invention. Furthermore, the organic electroluminescent device with a single organic layer or the organic electroluminescent device stacked as disclosed in US Patent No. 5,707,745, the entire contents of which are cited in the present invention.

Unless otherwise limited, any layer in different embodiments can be deposited and formed using any appropriate method. As far as the organic layer is concerned, preferred methods include thermal evaporation and spray printing as 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. 6,337,102 Method (organic vapor phase deposition, OVPD), the entire content of which is cited in the present invention; the organic vapor phase deposition method (deposition by organic vapor jet printing, OVJP) disclosed in US Patent No. 10/233470, the entire content of which is Quoted in this invention. Other suitable methods include spin coating and solution-based processes. The solution-based process is preferably carried out in a nitrogen or inert gas environment. For other layers, the preferred method includes thermal evaporation. The preferred patterning method includes the process of mask deposition and then cold welding as disclosed in US Patent Nos. 6,294,398 and 6,468,819, and the process of integrated spray printing or organic vapor spray deposition and patterning, all of which are based on this invention. Ming cited. Of course, other methods can also be used. The material used for deposition can be adjusted to correspond to the specific deposition method used.

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

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

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

Synthesis Example 1: Synthesis of Compound 1-1

Combine N-phenyl-3-carbazole boronic acid (10.0 g, 34.8 millimoles), 2-chloro-4,6-diphenyl-1,3,5-triazine (18.7 g, 70.0 millimoles) , Tetra(triphenylphosphine) palladium (2.0 g, 1.74 millimoles) and tetrahydrofuran (250 ml) in order Add 500ml double neck round bottom reaction flask, then add 50ml 2M potassium carbonate aqueous solution and fill the reaction system with nitrogen, heat the system with oil bath to reflux, after 16 hours of reaction, cool the system and filter the suspended matter After removing, rinse with tetrahydrofuran (300 ml) in batches, remove the aqueous layer in the filtrate and wash the organic layer with saturated brine, then remove the solvent with anhydrous magnesium sulfate and use a cyclotron concentrator to remove the solvent and use the crude product. The heavy tetrahydrofuran was dissolved in the crude product, and was added dropwise to 15 times the weight of the crude product in hexane to recrystallize. A white solid was obtained as compound 1-1 (12.0 g, 72%).

¹ H NMR (CDCl ₃ , 400MHz): δ 7.32 (dt, J=6.0, 0.8 Hz, 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

Combine 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-carbazole (20.0 g, 71.1 millimoles), 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) Sequentially add 1 liter double neck round bottom reaction flask, and then add 100 ml of 2M potassium carbonate aqueous solution and fill the reaction system with nitrogen. The system is heated to reflux in an oil bath. After 16 hours of reaction, the system is cooled and filtered to suspend. The substance was filtered off, and then tetrahydrofuran (300 ml) Wash in batches, remove the aqueous layer in the filtrate and wash the organic layer with saturated brine, then use anhydrous magnesium sulfate to remove water, use a cyclotron to remove the solvent, use tetrahydrofuran equal to the crude product to dissolve the crude product, and drop Adding 15 times the weight of the crude product to hexane for recrystallization, a white-like solid can be obtained as compound 2-1-1 (13.7 g, 53%).

Combine carbazole (20.0 g, 119.6 millimoles), 1-bromo-4-iodobenzene (38.0 grams, 134.3 millimoles), cuprous (I) chloride (2.37 grams, 23.9 millimoles), dimethyl Sulfide (250ml), potassium carbonate (33.1g, 239.2mmol) and 1,2-diaminocyclohexane (6.8g, 59.8mmol) were added to 500ml of double-necked round bottom in order to react The reaction system was filled with nitrogen, and the system was heated to 110°C in an oil bath. After 16 hours of reaction, the system was cooled down and the reactants were poured into 300 ml of water and stirred, and then extracted with ethyl acetate. Saturated brine was quenched, then magnesium sulfate was used to remove water and filtered. The resulting filtrate was used to remove the solvent with a cyclotron concentrator, and then silica gel column chromatography with hexane was used as the extraction system to obtain a light brown solid that was compound 2- 1-b (15.7 g, 41%).

Compound 2-1-1 (5.00 g, 12.55 millimoles), compound 2-1-1 (4.04 g, 12.55 millimoles), palladium acetate (0.06 g, 0.25 millimoles), toluene (150 ml) , Sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) 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 150 ml of ethyl acetate was added to stir. Then the reactant was filtered, and then washed with ethyl acetate (300 ml) in batches. The solid was dissolved in tetrahydrofuran. After filtering, the obtained filtrate was used to remove the solvent with a cyclotron concentrator. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, the off-white solid was obtained as compound 2-1 (6.13 g, 76%).

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 millimoles), 1-bromo-3-iodobenzene (38.0 grams, 134.3 millimoles), cuprous (I) chloride (2.37 grams, 23.9 millimoles), dimethyl Sulfide (250ml), potassium carbonate (33.1g, 239.2mmol) and 1,2-diaminocyclohexane (6.8g, 59.8mmol) were added to 500ml of double-necked round bottom in order to react The reaction system was filled with nitrogen, and the system was heated to 110°C in an oil bath. After 16 hours of reaction, the system was cooled down and the reactants were poured into 300 ml of water and stirred, and then extracted with ethyl acetate. Saturated brine was quenched, then magnesium sulfate was used to remove water and filtered. The resulting filtrate was used to remove the solvent with a cyclotron concentrator, and then silica gel column chromatography with hexane was used as the extraction system to obtain a light brown solid that was compound 2- 3-b (17.61 g, 46%).

Compound 2--1-a (5.00 g, 12.55 millimoles), compound 2-3-1 (4.04 g, 12.55 millimoles), palladium acetate (0.06 g, 0.25 millimoles) Mol), xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) were added to 250 milliliters of double-necked round bottom in order to react The reaction system was filled with nitrogen, and the system was heated to reflux with an oil bath. After 16 hours of reaction, the system was cooled and 150 ml of ethyl acetate was added to stir, then the reaction was filtered, and then divided with ethyl acetate (300 ml). After batch washing, the solid was dissolved in tetrahydrofuran and then filtered. The obtained filtrate was removed with a cyclotron concentrator to remove the solvent. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, the off-white 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 2-1-1 (7.50 g, 18.82 millimoles), 1,4-diiodobenzene (3.10 g, 9.41 millimoles), palladium acetate (0.08 g, 0.38 millimoles), Xylene (150 mL), sodium tert-butoxide (3.60 g, 37.46 mmol) and tri-tert-butyl phosphine (0.30 g, 1.51 mmol) were added to a 250 mL double-necked round bottom reaction flask in sequence, and The reaction system was filled with nitrogen, and the system was heated to reflux in an oil bath. After 16 hours of reaction, the temperature of the system was cooled and 150 ml of ethyl acetate was added to stir. Then the reactants were filtered and rinsed with tetrahydrofuran (300 ml) in batches. Purification with tetrahydrofuran extraction method with tetrahydrofuran, can obtain off-white solid compound 2-4 (6.13 g, 74%).

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

Combine 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 Millimoles), copper(I) iodide (4.55 g, 23.9 millimoles), dimethyl sulfite (250 ml), potassium carbonate (33.1 g, 239.2 millimoles), and 1,2-diamine Cyclohexane (6.8 g, 59.8 millimoles) was sequentially added to a 500 ml double-necked round bottom 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 down after 16 hours of reaction. The reactant was poured into 300 ml of water and stirred, and then extracted with ethyl acetate, the extract was quenched with saturated brine, and the water was removed with magnesium sulfate and filtered. The resulting filtrate was removed with a cyclotron concentrator to remove the solvent. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, a light brown solid can be obtained as compound 2-5-b (41.9 g, 80%).

Compound 2-1-1 (5.00 g, 12.55 millimoles), compound 2-5-b (5.50 grams, 12.55 millimoles), bis(dibenzylacetyl) palladium (0.14 grams, 0.25 millimoles) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) were sequentially added to a 250 ml double-necked round bottom reaction flask, and Fill the reaction system with nitrogen, heat the system to reflux in an oil bath, cool the system after 16 hours of reaction and add 150 ml of ethyl acetate to stir, then filter the reactant, and then rinse with ethyl acetate (300 ml) in batches , The solid was dissolved in tetrahydrofuran and then filtered. The filtrate was removed with a cyclotron concentrator to remove the solvent. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, an off-white solid was obtained as compound 2-5 (7.12 Grams, 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

Combine 9,10-dihydro-9,9-dimethylacridine (25.0 g, 119.6 millimoles), 1-bromo-4-iodobenzene (38.0 g, 134.3 millimoles), cuprous chloride ( I) (2.37 g, 23.9 millimoles), dimethyl sulfoxide (250 ml), potassium carbonate (33.1 g, 239.2 millimoles) and 1,2-diaminocyclohexane (6.8 g, 59.8 milliliters) Mol) sequentially add 500 ml double neck round bottom reaction flask, and fill the reaction system with nitrogen, heat the system to 110°C in an oil bath, after 16 hours of reaction, cool the system and pour the reactants into 300 ml water and stir After extracting with ethyl acetate, the extract was quenched with saturated brine, then magnesium sulfate was used to remove water and filtered. The resulting filtrate was removed with a cyclotron concentrator to remove the solvent, and then silica gel column chromatography with hexane was used as With the extraction system, a light brown solid can be obtained as compound 2-6-b (9.15 g, 21%).

Compound 2-1-1 (5.00 g, 12.55 millimoles), compound 2-6-b (4.57 grams, 12.55 millimoles), bis(dibenzylacetyl)palladium (0.14 grams, 0.25 millimoles), xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) were sequentially added to 250 ml of double neck The bottom reaction flask was filled with nitrogen. The system was heated to reflux in an oil bath. After 16 hours of reaction, the system was cooled down and 150 ml of ethyl acetate was added to stir. Then the reaction was filtered, and then ethyl acetate (300 ml ) After washing in batches, dissolve the solids in tetrahydrofuran and then filter. The filtrate obtained is used to remove the solvent with a cyclotron concentrator. Use silica gel column chromatography with ethyl acetate and hexane as the extraction system to obtain an off-white solid that is 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

Combine 4-(N-(naphthalene-1-yl)-N-anilino) phenylboronic acid (30.0 g, 44.2 millimoles), 4-chlorobromobenzene (9.3 g, 48.7 millimoles), tetrakis(triphenyl) Phosphine) palladium (1.0 g, 0.9 mmol) and tetrahydrofuran (400 ml) were sequentially added to a 1 liter double-necked round bottom reaction flask, and then 150 ml of 2M potassium carbonate aqueous solution was added and the reaction system was filled with nitrogen. Heat to reflux in an oil bath, After 16 hours of reaction, the system was cooled and filtered. The suspended matter 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. The water was removed with anhydrous magnesium sulfate and the solvent was removed with a cyclotron concentrator. Finally, using silica gel column chromatography with hexane extraction system, the off-white to light brown solid can be obtained as compound 2-8-b (17.7 g, 97%).

Compound 2-1-1 (5.00 g, 12.55 millimoles), compound 2-8-b (5.64 grams, 12.55 millimoles), bis(dibenzylacetyl)palladium (0.14 grams, 0.25 millimoles) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) were sequentially added to a 250 ml double-necked round bottom reaction flask, and Fill the reaction system with nitrogen, heat the system to reflux in an oil bath, cool the system after 60 hours of reaction and add 150 ml of ethyl acetate to stir, then filter the reactant, and then rinse with ethyl acetate (300 ml) in batches , The solid was dissolved in tetrahydrofuran and then filtered. The filtrate was removed with a cyclotron concentrator to remove the solvent. Using silica gel column chromatography with ethyl acetate and hexane as the extraction system, the off-white solid was obtained as compound 2-8 (5.40 Grams, 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) into a 250 mL double-necked round bottom reaction flask in sequence, and Fill the reaction system with nitrogen, heat the system to 70°C in 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 reactant 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 saturated eye water, and then concentrated And chromatograph with a silica gel tube to get the off-white solid compound 3--1-b (13.1 g, 60%).

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

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 2-1-1 (5.00 g, 12.55 millimoles), 3-bromo-N-phenyl-carbazole (4.04 g, 12.55 millimoles), palladium acetate (0.06 g, 0.25 millimoles), Toluene (100 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) were added to a 250 ml double-necked round-bottomed reaction flask in sequence, and nitrogen Fill the reaction system, and oil the system The bath was heated to reflux. After the reaction for 16 hours, the system was cooled and 150 ml of ethyl acetate was added to stir, then the reactant was filtered, and then washed with ethyl acetate (300 ml) in batches, and the solid was dissolved in tetrahydrofuran and filtered. The solvent was removed from the filtrate with a cyclotron concentrator, and tetrahydrofuran and hexane were used as recrystallization to obtain an off-white solid compound 4-1 (4.98 g, 62%).

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) into a 250 mL double-necked round bottom reaction flask in sequence , And fill the reaction system with nitrogen, heat the system to 70°C in an oil bath and stir for 30 minutes, then add 2-chloro-4,6-diphenylpyrimidine (10.8 g, 40.6 millimoles) and another 50 ml of Dimethyl acetamide, after 16 hours of reaction, the system is cooled down and the reactants are filtered and washed with 50 ml of dimethyl acetamide and 100 ml of tetrahydrofuran, and then the solid in the white porcelain funnel is washed with a large amount of water. Pour the remaining solid in 200 ml of tetrahydrofuran and heat to 65° C. and stir for 30 minutes. Filter while hot to obtain a white solid compound 4-3-b (14.9 g, 68%).

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

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, 2.4 Hz, 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) into a 250 mL double-necked round bottom reaction flask in sequence , And fill the reaction system with nitrogen, heat the system to 70°C in an oil bath and stir for 30 minutes, then add 2-chloro-4,6-diphenylpyrimidine (10.8 g, 40.6 millimoles) and another 50 ml of Dimethyl acetamide, after 16 hours of reaction, the system is cooled down and the reactants are filtered and washed with 50 ml of dimethyl acetamide and 100 ml of tetrahydrofuran, and then the solid in the white porcelain funnel is washed with a large amount of water. Pour the remaining solid in 200 ml of tetrahydrofuran and heat to 65° C. and stir for 30 minutes. Filter while hot to obtain a white solid compound 4-4-b (14.9 g, 97%).

Compound 2-1-1 (5.00 g, 12.55 millimoles), compound 4-3-b (5.98 g, 12.55 millimoles), bis(dibenzylacetyl) palladium (0.14 g, 0.25 millimoles) , Xylene (150 ml), sodium tert-butoxide (4.00 g, 41.62 millimoles) and tri-tert-butyl phosphine (0.25 g, 12.6 millimoles) in order Put into a 250 ml double-necked round bottom reaction flask and fill the reaction system with nitrogen. Heat the system with an oil bath to reflux. After 72 hours of reaction, cool the system and add 150 ml of ethyl acetate to stir, then filter the reactants, and then After rinsing in batches with ethyl acetate (300 ml), the solid was dissolved in tetrahydrofuran and then filtered. The filtrate was removed with a cyclotron concentrator to remove the solvent, and tetrahydrofuran and hexane were used as recrystallization to obtain an off-white solid called 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.

Table 4 shows the physical property values of the above-mentioned materials. The measuring methods of each physical property value are as follows.

(1) Thermal cracking temperature (T _d )

A thermogravimetric analyzer (Perkin Elmer, TGA 8000) was used for measurement. Under normal pressure and a nitrogen atmosphere, the thermal pyrolysis properties of the prepared compounds were measured at a temperature program 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 temperature program rate of 20°C/min.

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

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

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

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

(5) Triplet energy value (E _T )

Measure the luminescence spectrum with a fluorescence spectrometer (Perkin Elmer, LS 55) at a temperature of 77K, and then calculate it to obtain E _T.

(6) Peak wavelength of emitted light (PL)

The fluorescence spectra of each synthesis example in the tetrahydrofuran solution state were measured with a light-excited fluorescence spectrometer (Perkin Elmer, LS 55), and the measurement conditions were: the concentration was 10 ^-5 M, and the measurement range was 300 to 800 nm.

Example 1: Manufacturing of organic electroluminescent device

Before the substrate is loaded into the evaporation system for use, the substrate is cleaned with 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, thickness 20nm, including 9% p doped Type electrically conductive dopant HTM, wherein the p-type electrically conductive dopant is purchased from Shanghai Hanfeng Chemical Co., Ltd., and the HTM is purchased from Merck & Co., Inc.; b) hole transport layer, Thickness of 140nm, HTM; c) Exciton blocking layer, thickness of 10nm, HT (made by Yulei Optoelectronics); d) Light-emitting layer, thickness of 30nm, including doped with 4% volume ratio PER (Yuelei Optoelectronics) Preparation) Compound 1-1; e) Electron transport layer, thickness 30nm, containing compound ET-1 (produced by Yulei Optoelectronics) and doped lithium quinolate (Liq, produced by Yulei Optoelectronics); f) Electron injection Layer, thickness 0.5nm, LiF; and g) cathode, thickness about 150nm, Al.

The device 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)/ET-1: Liq(30nm)/LiF(0.5nm)/Al(150nm).

After the above-mentioned layers are deposited and formed, the device is transported from the deposition chamber to the drying box, and then encapsulated with a UV curable epoxy resin and a glass cover plate containing a moisture absorbent. The organic electroluminescence element has a light-emitting area of 9 square millimeters.

Examples 2 to 8: Manufacturing of organic electroluminescent devices

Except that the compound 1-1 of the light-emitting layer in Example 1 was replaced with a compound 物 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 are the same as 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: Manufacturing of Organic Electroluminescent Devices

The organic electroluminescence element was set 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 compound EPH-1 and EPH-2/HT composition (weight ratio 1:1 ), EPH-1 is a material in our company’s patent number US 8,592,055 B2, prepared by Yulei Optoelectronics, EPH-2 is a material in Nippon Steel & Sumikin Chemical’s patent number US 8,993,129 B2, prepared by Yulei Optoelectronics, comparative example 1 and Comparative Example 2 has the same layer structure as Example 1, and the doping volume of its guest material PER is shown in Table 5.

The electroluminescence properties of the organic electroluminescence elements made above are all Use 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.) to measure at room temperature Its luminous properties, its driving voltage and luminous efficiency are listed in Table 5.

As mentioned above, within the acceptable driving voltage range, it can be seen that the organic electroluminescent device comprising the carbazole-substituted triazine compound with the structure of the present invention exhibits good heat resistance and significantly improves its luminous efficiency Therefore, the organic electroluminescent element of the present invention is suitable for automotive displays and other application fields, and has extremely high technical value.

The above-mentioned embodiments are only illustrative and not used to limit the present invention. Anyone familiar with this technique can modify and change the above-mentioned 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 the technical content of this disclosure.

200‧‧‧Organic electroluminescence element

210‧‧‧Substrate

220‧‧‧Anode

230‧‧‧hole injection layer

240‧‧‧Hole Transmission Layer

250‧‧‧Light-emitting layer

260‧‧‧Electron transport layer

270‧‧‧Electron injection layer

280‧‧‧Cathode

245‧‧‧ exciton barrier

Claims (15)

A carbazole-substituted triazine compound with the structure of formula (I):

Wherein, Ar ₁ are the same or different, and each Ar ₁ independently represents hydrogen, a C _1-8 alkyl group, and a substituted or unsubstituted C _6-30 aryl group; m represents an integer of 1 or 2; n represents An integer from 0 to 2; where n is 0, L represents a substituted or unsubstituted C _5-12 aryl group, and a substituted or unsubstituted C _5-12 aryl group selected from the group consisting of N, O, and S And when n is 1 or 2, L represents a substituted or unsubstituted C _5-12 aryl group and a substituted or unsubstituted C _3-40 heteroaryl group; A C _3-40 heteroaryl group free from at least one heteroatom in the group consisting of N, O, and S; Z ₁ represents hydrogen, cyano, C _1-8 alkyl, substituted or unsubstituted C _5-12 aryl groups, and substituted or unsubstituted C _3-40 heteroaryl groups containing at least one heteroatom selected from the group consisting of N, O, and S; and X ₁ represents the formula (I -1) or formula (I-2) structure:

Wherein, 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 of R ₂ and R ₃ independently represents hydrogen, cyano, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted containing selected from N, O, and C _3-40 heteroaryl group of at least one heteroatom in the group consisting of S; and f represents an integer from 0 to 2; wherein, the substituted substituents are each independently selected from the group consisting of at least one of: deuterium, halo, C _1-30 alkyl, C _1-30 alkoxy, C _6-30 aryl, C _5-30 heteroaryl, C _6-30 aryl substituted by the group C _{5 -30} heteroaryl, benzimidazolyl, C _3-30 cycloalkyl, C _5-7 heterocycloalkyl, tri-C _1-30 alkylsilyl, tri-C _1-30 arylsilyl, diC _1-30 Alkyl C _{6-30 Arylsilyl} , C _1-30 Alkyl, C _{6-30 Arylsilyl} , C _2-30 Alkenyl, C _2-30 Alkynyl, Cyano, Di-C _{1 -30} alkylamino group, two C _6-30 aryl boron group, two C _1-30 alkyl boron group, C _1-30 alkyl group, C _6-30 aryl group C _1-30 alkyl group, C _{1- 30} alkyl C _6-30 aryl, carboxyl, nitro and hydroxyl. The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of patent application is represented by the structure of formula (II):

The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of patent application, wherein X ₁ is selected from one of the following groups:

The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of 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 It is selected from substituted or unsubstituted phenylene, biphenylene or pyrimidinyl. The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of patent application, wherein Z ₁ is a substituted triazine group. The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of the patent application, wherein, when m is 1 and n is 0, L is a phenyl group. The carbazole-substituted triazine compound having the structure of formula (I) as described in item 6 of the scope of patent application, wherein the compound of formula (I) represents compound (1-2),

The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of the patent application, wherein when m is 1 and n is 1, L is phenylene or biphenylene. The carbazole-substituted triazine compound with the structure of formula (I) as described in item 8 of the scope of patent application, wherein the compound of formula (I) represents compound (2-8),

The carbazole-substituted triazine compound with the structure of formula (I) as described in item 1 of the scope of 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 with the structure of formula (I) as described in item 10 of the scope of patent application, wherein L is a phenyl group or a substituted pyrimidinyl group. The carbazole-substituted triazine compound with the structure of formula (I) as described in item 11 of the scope of patent application, wherein the compound of formula (I) represents compound (4-1),

An organic electroluminescence element, comprising: a cathode; The anode; and the organic layer is between the cathode and the anode, and the organic layer includes the triazine compound with the structure of formula (I) as described in item 1 of the scope of patent application. According to the organic electroluminescent device described in item 13 of the scope of the patent application, the organic layer is a light-emitting layer, and the thickness thereof is 20 nm to 40 nm. The organic electroluminescent device according to claim 14, wherein the light-emitting layer contains a guest material, and based on the total weight of the light-emitting layer, the content of the guest material is 2% to 8% by weight .

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