An organic compound and its application and an organic electroluminescent device using the compound

Abstract

The present invention relates to a novel organic compound, and also to a compound used in an organic electroluminescent device and an organic electroluminescent device using the compound. The novel organic compound of the present invention has the following structure: wherein: Ar 1 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; X is selected from CR 1 R 2 , O, S or SiR 3 R 4 ; R a , R b , R n are independently selected from the group consisting of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and R a , R b , R n At least one of the structures is represented by formula (Hy). When the compound of the present invention is used as a luminescent dye and / or sensitizer in an OLED device, it exhibits excellent device performance and stability. The present invention also protects an organic electroluminescent device using the compound of the above general formula.

Description

Technical Field

[0001] The present invention relates to a novel organic compound, in particular to a compound used for an organic electroluminescent device and an organic electroluminescent device using the compound. Background Art

[0002] Organic optoelectronic devices have received increasing attention in recent years. Compared with inorganic devices, they have potential cost advantages because the materials they use are cheaper. Among them, organic light-emitting diodes (OLED: Organic Light Emission Diodes) are a type of device with a sandwich-like structure. Its working principle is to sandwich an organic functional material layer between the positive and negative electrode film layers. When the device is working, positive charges are injected from the positive electrode and negative charges are injected from the negative electrode. Under the action of the electric field, the positive and negative charges migrate in the organic layer and meet to compound and emit light. Due to the advantages of high brightness, fast response, wide viewing angle, simple process, and flexibility, OLED devices have attracted much attention in the fields of new display technology and new lighting technology. At present, this technology has been widely used in display panels of new lighting fixtures, smart phones, tablet computers and other products, and will further expand to the application fields of large-size display products such as TVs. It is a new display technology with fast development and high technical requirements.

[0003] As the core material in OLED devices, luminescent materials have received more research and attention. At present, in the structure of organic electroluminescent devices in the field of display and lighting, red and green light luminescent materials usually use phosphorescent materials, while blue light materials usually use fluorescent materials due to problems such as material matching and life span. Recently, a literature has reported an ultra-pure blue fluorescent dye BN compound based on TADF (Thermally Activated Delayed Fluorescence), as shown in the figure below. The compound is based on a rigid polycyclic aromatic skeleton, connected by B atoms and N atoms at key sites. Due to the opposite resonance effects of B atoms and N atoms, the HOMO orbital and LUMO orbital of the compound are separated in space, and the HOMO orbital is distributed on the N atom and its ortho-para carbon atoms, while the LUMO orbital is distributed on the B atom and its ortho-para carbon atoms, so that the compound has TADF properties and a narrower emission half-peak width. However, the LUMO energy level of this type of compound is too low, which will lead to direct recombination of excitons on the dye, forming a more serious quenching phenomenon, and serious efficiency roll-off at high brightness.

[0004] Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a new type of compound, which belongs to a thermally activated delayed fluorescent material. The present invention also provides an application method of the compound in an OLED device and an organic electroluminescent device using the compound.

[0006] The novel compound of the present invention has the general formula (1):

[0007]

[0008] In the general formula (1):

[0009] Ar 1 One selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups;

[0010] Further preferably, the Ar 1 is selected from the group consisting of substituted or unsubstituted phenyl, naphthyl, biphenyl, terphenyl, carbazolyl, furyl, thienyl, fluorenyl, pyridyl, bipyridyl, benzopyridyl, benzopyrimidyl, naphthyl, phenanthrenyl, quinolyl, isoquinolyl, quinazolinyl, triazinyl, pyrazinyl, pyridazinyl, benzimidazolyl, pyrimidinyl or o-phenanthroline. Most preferably, Ar 1 Selected from phenyl.

[0011] X is selected from CR 1 R 2 , O, S or SiR 3 R 4 ; R 1 , R 2 , R 3 and R 4 Each is independently selected from one of C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0012] R a , R b , R n Each independently represents a monosubstituted to maximum permissible substituent, and each independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and R a , R b , R n At least one of them is of formula (Hy);

[0013] Furthermore, the above R a , R b , R n Each of the following substituents is independently selected from the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, tetraphenylene, pentacene, benzopyrenyl, biphenylene, phenylene, terphenylene, triphenylene, quaternaryl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthroline, 1,2, 3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, or a combination of two of the above groups.

[0014] In the formula (Hy):

[0015] Ring A represents a single substitution to the maximum permissible substituent, and is fused to the benzene ring at at least one position among a, b and c. Ring A is selected from a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.

[0016] R i It represents monosubstituted to the maximum permissible substituent, selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.

[0017] When the above-mentioned groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic aromatic or condensed aromatic hydrocarbon groups, C3-C30 monocyclic heteroaryl or condensed heteroaryl groups.

[0018] It should be noted that, in the present invention, the maximum permissible substituent refers to the maximum number of substituents under the premise that the substituted group meets the requirements of the chemical bond. For example, a The connected ring can be connected to R a The number of can be one or more, but can only reach the maximum allowed substituents (i.e. 4).

[0019] In the present specification, the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent.

[0020] In the present specification, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0021] In the present specification, the substituted or unsubstituted C6-C30 aryl group is preferably a C6-C20 aryl group, more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, an indenyl group, a fluorenyl group and its derivatives, a fluoranthenyl group, a triphenylene group, a pyrenyl group, a peryl group, A group consisting of a tetraphenyl group and a naphthyl group. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl and 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl.

[0022] The heteroatom in the present invention generally refers to an atom or an atom group selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0023] In the present specification, the substituted or unsubstituted C3~C30 heteroaryl group is preferably a C4~C20 heteroaryl group, and more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazole and derivatives thereof, wherein the carbazole derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolecarbazole.

[0024] In the present specification, the C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, and more preferably a C1-C6 chain alkyl group, examples of which include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, and tert-butyl.

[0025] In the present specification, the C3-C12 cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, and preferably a C1-C10 alkyl group and a C3-C10 cycloalkyl group.

[0026] Furthermore, the general compound of the present invention is selected from one of the following formulas (2-1), (2-2), (2-3) or (2-4):

[0027]

[0028] More preferably, the general compound of the present invention is selected from formula (2-3) or (2-4).

[0029] More preferably, in the formula (1), formula (2-1), (2-2), (2-3) or (2-4) of the present invention, R n One of them is of formula (Hy); preferably, the Rn represents a monosubstituted group and is of the formula (Hy).

[0030] More preferably, in the formula (1), formula (2-1), (2-2), (2-3) or (2-4) of the present invention, R a One of them is of formula (Hy); or the R b One of them is of formula (Hy); or the R n There is a formula (Hy).

[0031] More preferably, the formula (Hy) of the present invention is preferably the following formula (Hy 1 ):

[0032]

[0033] Formula (Hy 1 ), the dotted line represents the site where the groups are fused, i.e., formula (A-1) and formula (Hy-1) are fused from site d to any of the three sites a, b or c, respectively;

[0034] E 1 Selected from CR 5 R 6 NR 7 , O, S or SiR 8 R 9 One of the 5 , R 6 , R 7 , R 8 and R 9 Each is independently selected from one of C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0035] R h , R g and R i Each independently represents a single substituent to the maximum permissible substituent, and is independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R h , R g or R i can be independently combined with the corresponding R g , R h or R iThe connected aromatic rings are fused to each other to form a substituted or unsubstituted C9-C30 aryl group or a substituted or unsubstituted C9-C30 heteroaryl group.

[0036] Further preferably, the formula (Hy 1 ) is selected from the following formula (Hy-1), (Hy-2), (Hy-3), (Hy-4) or (Hy-5):

[0037]

[0038] More preferably, formula (Hy) is selected from the following formula (Hy1), (Hy2), (Hy3) or (Hy4):

[0039]

[0040] Preferred structures of the compounds of the present invention include, but are not limited to, the following compounds represented by structures S1 to S170:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] As another aspect of the present invention, there is also provided an application of the compound as described above in an organic electroluminescent device. Specifically, it is preferably used as a light-emitting layer material in an organic electroluminescent device, and more preferably used as a light-emitting dye and / or sensitizer in the light-emitting layer of an organic electroluminescent device.

[0048] As another aspect of the present invention, an organic electroluminescent device is provided, comprising a first electrode, a second electrode and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer contains a compound of the general formula (1) as described above, or contains a compound having a structure shown in S1 to S170 as described above.

[0049] Specifically, one embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, and a first electrode, a plurality of light-emitting functional layers and a second electrode sequentially formed on the substrate; the light-emitting functional layers comprise a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a light-emitting layer is provided between the hole transport layer and the electron transport layer; wherein the light-emitting layer contains the general formula compound of the present invention represented by the above formula (1).

[0050] The present invention further discloses a display screen or a display panel, wherein the organic electroluminescent device as described above is adopted in the display screen or the display panel; preferably, the display screen or the display panel is an OLED display.

[0051] The present invention also discloses an electronic device, wherein the electronic device has a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescent device as described above.

[0052] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel manufacturing companies for high-performance materials.

[0053] The specific reasons why the above compounds of the present invention have excellent performance as luminescent dyes and / or sensitizer materials in the light-emitting layer of an organic electroluminescent device are not clear, but it is speculated that the reasons may be as follows:

[0054] The general compound provided by the present invention introduces a group with electron-pushing properties as shown in the structural formula Hy at the para position of boron in the molecular structure, thereby achieving an improvement in the LUMO energy level of the prepared compound and improving the hole transport performance of the compound to improve device performance.

[0055] The compound of the general formula provided by the present invention has the following beneficial effects:

[0056] 1. The boron atom contained in the compound of the present invention has a resonance effect with the nitrogen atom in the same ring, and the opposite resonance effect is enhanced at the para position. Therefore, this effect can clearly separate the HOMO and LUMO orbitals, thereby having thermally activated delayed fluorescence properties.

[0057] 2. The introduction of the electron-pushing group Hy into the compound structure of the present invention helps to adjust the energy level of the compound, adjust the charge distribution of the compound, and is conducive to further delocalization of electrons, thereby improving the fluorescence quantum yield of the compound and facilitating its use as a dye;

[0058] 3. The introduction of the electron-pushing group Hy into the compound structure of the present invention helps to cause the red shift of the compound emission spectrum, making it match the main material in the light-emitting layer, which is conducive to use as a dye;

[0059] 4. The electron-pushing group Hy is introduced into the compound structure of the present invention, which has a higher degree of matching with the main material in the light-emitting layer, helps to improve the hole transport performance of the compound, balance the carrier transport in the device, expand the exciton recombination area, and is conducive to improving the performance of the device;

[0060] 5. The introduction of X into the general structure of the compound of the present invention is beneficial to enhancing the rigidity of the molecule, improving the fluorescence quantum yield, and at the same time helping to improve the stability of the molecule.

[0061] In addition, the preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion. DETAILED DESCRIPTION

[0062] The specific preparation method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.

[0063] However, it should be noted that obtaining the compound is not limited to the synthesis method and raw materials used in the present invention, and those skilled in the art may also select other methods or routes to obtain the novel compound proposed in the present invention. The compounds for which the synthesis method is not mentioned in the present invention are raw materials obtained from commercial channels, or are prepared by these raw materials according to known methods.

[0064] The solvents and reagents used in the synthesis examples, such as dichloromethane, petroleum ether, ethanol, tetrahydrofuran, N, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and other chemical reagents, can be purchased from the domestic chemical product market, such as Sinopharm Group Reagent Company, TCI Company, Shanghai Bid Pharmaceutical Company, Bailingwei Reagent Company, etc. In addition, those skilled in the art can also synthesize by known methods.

[0065] The analysis and detection of the intermediates and compounds in the synthesis examples were performed using an ABSCIEX mass spectrometer (4000QTRAP).

[0066] The synthesis method of the compound of the present invention is briefly described below.

[0067] Synthesis Example

[0068] Representative synthetic routes:

[0069]

[0070] More specifically, the synthesis methods of representative compounds of the present invention are given below.

[0071] Synthesis Example

[0072] Synthesis Example 1: Synthesis of Compound S1

[0073]

[0074] Synthesis of intermediate S1-1:

[0075] At room temperature, add 2-chloro-3-isophenylpropyl-5-fluorobromobenzene (50g, 152.6mmol), N-phenylindole [2,3-a] carbazole (55.8g, 167.9mmol), cesium carbonate (44.2g, 228.9mmol), DMF (500ml) to a 1L single-mouth bottle, and react at 120°C overnight. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and silica gel column chromatography (PE) to obtain 82.3g of white solid product with a yield of 84%. The molecular ion mass determined by mass spectrometry is 639.04 (theoretical value: 639.03).

[0076] Synthesis of intermediate S1-2:

[0077] At room temperature, S1-1 (80 g, 125.2 mmol), diphenylamine (25.42 g, 150.2 mmol), Pd2(dba)3 (2.30 g, 2.50 mmol), tri-tert-butylphosphine (1.01 g, 5.01 mmol), sodium tert-butoxide (24.06 g, 250.4 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated by mixing with silica gel. 90 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 79 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 87%. The molecular ion mass determined by mass spectrometry was 727.30 (theoretical value: 727.35).

[0078] Synthesis of compound S1:

[0079] S1-2 (20.00 g, 27.5 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (20 ml, 1.6 M, 31 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (7.58 g, 30.1 mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45 ° C and stirred for 50 minutes. In an ice-water bath, N, N-diisopropylethylamine (7.1 g, 54.9 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120 ° C, and reacted overnight. The heating was stopped, and water (500 ml) was added to quench the mixture after the system cooled to room temperature. The lower organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate (500 ml). The organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, column chromatography was performed to obtain 9 g of crude product, and toluene / ethanol was used for recrystallization to obtain 5.25 g of yellow solid, with a yield of 27%. The molecular ion mass determined by mass spectrometry was 700.61 (theoretical value: 700.69).

[0080] Synthesis Example 2:

[0081] Synthesis of compound S11

[0082]

[0083] Synthesis of intermediate S11-1:

[0084] At room temperature, add 2-chloro-3-(4-tert-butylisophenylpropyl)-5-fluorobromobenzene (58.3g, 152.6mmol), N-phenylindole [3,2-c] carbazole (55.8g, 167.9mmol), cesium carbonate (44.2g, 228.9mmol), DMF (500ml) to a 1L single-mouth bottle, and react overnight at 120℃. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and mix with silica gel column chromatography (PE) to obtain 94.7g of white solid product with a yield of 89%. The molecular ion mass determined by mass spectrometry is: 696.18 (theoretical value: 696.18).

[0085] Synthesis of intermediate S11-2:

[0086] At room temperature, S11-1 (86.9 g, 125.2 mmol), di-4-tert-butylaniline (42.35 g, 150.2 mmol), Pd2(dba)3 (2.30 g, 2.50 mmol), tri-tert-butylphosphine (1.01 g, 5.01 mmol), sodium tert-butoxide (24.06 g, 250.4 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 99 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 86.2 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 77%. The molecular ion mass determined by mass spectrometry was 726.34 (theoretical value: 727.35).

[0087] Synthesis of compound S11:

[0088] S11-2 (27.65 g, 27.5 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (20 ml, 1.6 M, 31 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (7.58 g, 30.1 mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45 ° C and stirred for 50 minutes. In an ice-water bath, N, N-diisopropylethylamine (7.1 g, 54.9 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120 ° C, and reacted overnight. The heating was stopped, and water (500 ml) was added to quench the mixture after the system cooled to room temperature. The lower organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate (500 ml). The organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, and 11 g of crude product was obtained by column chromatography, and 5.73 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 21%. The molecular ion mass determined by mass spectrometry was 869.99 (theoretical value: 870.00).

[0089] Synthesis Example 3: Synthesis of Compound S37

[0090]

[0091] Synthesis of intermediate S37-1:

[0092] At room temperature, add 2-chloro-3-bromo-5-fluorophenol (50g, 221.7mmol), p-fluorotoluene (26.9g, 243.9mmol), potassium carbonate (61.3g, 443.6mmol), DMF (500ml) to a 2L single-mouth bottle, and react at 120°C overnight. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and perform silica gel column chromatography (PE) to obtain 61.2g of white solid product with a yield of 87%. The molecular ion mass determined by mass spectrometry is 315.57 (theoretical value: 315.57).

[0093] Synthesis of intermediate S37-2:

[0094] At room temperature, S37-1 (50 g, 158.5 mmol), benzofurano[3,2-b]carbazole (44.8 g, 174.3 mmol), cesium carbonate (45.8 g, 237.7 mmol), DMF (500 ml) were added to a 1 L single-mouth bottle, and the mixture was reacted at 120°C overnight. The heating was stopped, and after cooling to room temperature, 500 ml of water was added, and the mixture was extracted with 500 ml of dichloromethane, dried over anhydrous sodium sulfate, and subjected to silica gel column chromatography (PE) to obtain 81.1 g of a white solid product with a yield of 82%. The molecular ion mass determined by mass spectrometry was 552.83 (theoretical value: 552.85).

[0095] Synthesis of intermediate S37-3:

[0096] At room temperature, S37-2 (80 g, 144.7 mmol), xylidine (34.26 g, 173.7 mmol), Pd2(dba)3 (2.65 g, 2.89 mmol), tri-tert-butylphosphine (1.17 g, 5.79 mmol), sodium tert-butoxide (27.81 g, 289.4 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 96 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 72 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 74%. The molecular ion mass determined by mass spectrometry was 669.21 (theoretical value: 669.22).

[0097] Synthesis of compound S37:

[0098] S37-3 (20.00 g, 29.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (21 ml, 1.6 M, 32 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (8.24 g, 32.87 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (7.73 g, 59.77 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 11 g of crude product was obtained by column chromatography. 5.63 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 29%. The molecular ion mass determined by mass spectrometry was 642.57 (theoretical value: 642.57).

[0099] Synthesis Example 4: Synthesis of Compound S42

[0100]

[0101] Synthesis of intermediate S42-1:

[0102] At room temperature, add 2-chloro-3-bromo-5-fluorophenol (50g, 221.7mmol), p-fluorotert-butylbenzene (37.1g, 243.9mmol), potassium carbonate (61.3g, 443.6mmol), DMF (500ml) to a 2L single-mouth bottle, and react at 120°C overnight. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and silica gel column chromatography (PE) to obtain 77.3g of white solid product with a yield of 97%. The molecular ion mass determined by mass spectrometry is: 357.64 (theoretical value: 357.65).

[0103] Synthesis of intermediate S42-2:

[0104] At room temperature, S42-1 (56.58 g, 158.5 mmol), benzofurano[3,2-c]carbazole (44.8 g, 174.3 mmol), cesium carbonate (45.8 g, 237.7 mmol), DMF (500 ml) were added to a 1 L single-mouth bottle, and the mixture was reacted at 120°C overnight. The heating was stopped, and after cooling to room temperature, 500 ml of water was added, and the mixture was extracted with 500 ml of dichloromethane, dried over anhydrous sodium sulfate, and subjected to silica gel column chromatography (PE) to obtain 87.1 g of a white solid product with a yield of 92%. The molecular ion mass determined by mass spectrometry was 593.96 (theoretical value: 593.93).

[0105] Synthesis of intermediate S42-3:

[0106] At room temperature, S42-2 (85.95 g, 144.7 mmol), di-tert-butylaniline (48.98 g, 173.7 mmol), Pd2(dba)3 (2.65 g, 2.89 mmol), tri-tert-butylphosphine (1.17 g, 5.79 mmol), sodium tert-butoxide (27.81 g, 289.4 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. Column chromatography (PE: EA = 100: 1) obtained 104 g of crude product, and toluene / ethanol recrystallization obtained 88 g of white solid, with a yield of 76%. The molecular ion mass determined by mass spectrometry was: 795.41 (theoretical value: 795.45).

[0107] Synthesis of compound S42:

[0108] S42-3 (23.78 g, 29.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (21 ml, 1.6 M, 32 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (8.24 g, 32.87 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (7.73 g, 59.77 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 20 g of crude product was obtained by column chromatography. 6.72 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 29%. The molecular ion mass determined by mass spectrometry was 768.80 (theoretical value: 768.81).

[0109] Synthesis Example 5: Synthesis of Compound S64

[0110]

[0111] Synthesis of intermediate S64-1:

[0112] At room temperature, add 2-chloro-3-p-tert-butylphenylthio-5-fluorobromobenzene (50g, 133.8mmol), indeno[2,3-a]carbazole (41.7g, 147.2mmol), cesium carbonate (38.72g, 200.7mmol), DMF (500ml) to a 1L single-mouth bottle, and react at 120℃ overnight. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and silica gel column chromatography (PE) to obtain 82.7g of white solid product with a yield of 98%. The molecular ion mass determined by mass spectrometry is: 637.07 (theoretical value: 637.08).

[0113] Synthesis of intermediate S64-2:

[0114] At room temperature, S64-1 (80 g, 125.6 mmol), di-tert-butylaniline (42.41 g, 150.7 mmol), Pd2(dba)3 (2.30 g, 2.51 mmol), tri-tert-butylphosphine (1.02 g, 5.02 mmol), sodium tert-butoxide (24.14 g, 251.2 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 92 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 80 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 76%. The molecular ion mass determined by mass spectrometry was 837.54 (theoretical value: 837.61).

[0115] Synthesis of compound S64:

[0116] S64-2 (20.00 g, 23.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (19 ml, 1.6 M, 27 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (6.58 g, 26.27 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (6.17 g, 47.76 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 7 g of crude product was obtained by column chromatography. 4.99 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 24%. The molecular ion mass determined by mass spectrometry was 810.90 (theoretical value: 810.95).

[0117] Synthesis Example 6: Synthesis of Compound S73

[0118]

[0119] Synthesis of intermediate S73-1:

[0120] At room temperature, add 2-chloro-3-p-tert-butylphenylthio-5-fluorobromobenzene (50g, 133.8mmol), benzothieno[3,2-c]carbazole (40.19g, 147.2mmol), cesium carbonate (38.72g, 200.7mmol), DMF (500ml) to a 1L single-mouth bottle, and react overnight at 120℃. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and mix with silica gel column chromatography (PE) to obtain 83.4g of white solid product with a yield of 99%. The molecular ion mass determined by mass spectrometry is: 625.00 (theoretical value: 625.03).

[0121] Synthesis of intermediate S73-2:

[0122] At room temperature, S73-1 (78.5 g, 125.6 mmol), di-tert-butylaniline (42.41 g, 150.7 mmol), Pd2(dba)3 (2.30 g, 2.51 mmol), tri-tert-butylphosphine (1.02 g, 5.02 mmol), sodium tert-butoxide (24.14 g, 251.2 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated by mixing with silica gel. 92 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 79 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 76%. The molecular ion mass determined by mass spectrometry was 827.55 (theoretical value: 827.59).

[0123] Synthesis of compound S73:

[0124] S73-2 (19.78 g, 23.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (19 ml, 1.6 M, 27 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (6.58 g, 26.27 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (6.17 g, 47.76 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 9 g of crude product was obtained by column chromatography. 5.01 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 25%. The molecular ion mass determined by mass spectrometry was 800.33 (theoretical value: 800.34).

[0125] Synthesis Example 7: Synthesis of Compound S74

[0126]

[0127] Synthesis of intermediate S74-1:

[0128] At room temperature, add 2-chloro-3-p-tert-butylphenylthio-5-fluorobromobenzene (50g, 133.8mmol), indeno[3,2-c]carbazole (41.7g, 147.2mmol), cesium carbonate (38.72g, 200.7mmol), DMF (500ml) to a 1L single-mouth bottle, and react at 120℃ overnight. Stop heating, add 500ml of water after cooling to room temperature, extract with 500ml of dichloromethane, dry with anhydrous sodium sulfate, and silica gel column chromatography (PE) to obtain 84.6g of white solid product with a yield of 99%. The molecular ion mass determined by mass spectrometry is: 637.07 (theoretical value: 637.08).

[0129] Synthesis of intermediate S74-2:

[0130] At room temperature, S74-1 (80 g, 125.6 mmol), di-tert-butylaniline (42.41 g, 150.7 mmol), Pd2(dba)3 (2.30 g, 2.51 mmol), tri-tert-butylphosphine (1.02 g, 5.02 mmol), sodium tert-butoxide (24.14 g, 251.2 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated by mixing with silica gel. Column chromatography (PE: EA = 100: 1) was performed to obtain 100 g of crude product, which was recrystallized from toluene / ethanol to obtain 88 g of white solid, with a yield of 84%. The molecular ion mass determined by mass spectrometry was 837.54 (theoretical value: 837.61).

[0131] Synthesis of compound S74:

[0132] S74-2 (20.00 g, 23.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (19 ml, 1.6 M, 27 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (6.58 g, 26.27 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (6.17 g, 47.76 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 8 g of crude product was obtained by column chromatography. 5.12 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 26%. The molecular ion mass determined by mass spectrometry was 810.90 (theoretical value: 810.95).

[0133] Synthesis Example 8: Synthesis of Compound S148

[0134]

[0135] Synthesis of intermediate S148-1:

[0136] At room temperature, 2-chloro-3-bromo-5-fluorophenyl-p-tert-butylphenylthiodiphenylsilane (50 g, 95.4 mmol), benzocarbazole (22.8 g, 105.0 mmol), cesium carbonate (27.61 g, 143.2 mmol), DMF (500 ml) were added to a 1L single-mouth bottle, and the mixture was reacted at 120°C overnight. The heating was stopped, and after cooling to room temperature, 500 ml of water was added, and the mixture was extracted with 500 ml of dichloromethane, dried over anhydrous sodium sulfate, and subjected to silica gel column chromatography (PE) to obtain 62.8 g of a white solid product with a yield of 91%. The molecular ion mass determined by mass spectrometry was 721.20 (theoretical value: 721.21).

[0137] Synthesis of intermediate S148-2:

[0138] At room temperature, S148-1 (60 g, 83.2 mmol), di-tert-butylaniline (25.76 g, 91.51 mmol), Pd2(dba)3 (2.30 g, 2.51 mmol), tri-tert-butylphosphine (1.02 g, 5.02 mmol), sodium tert-butoxide (15.99 g, 166.4 mmol), and xylene (1000 ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 92 g of crude product was obtained by column chromatography (PE: EA = 100: 1), and 71 g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 93%. The molecular ion mass determined by mass spectrometry was 921.73 (theoretical value: 921.74).

[0139] Synthesis of compound S148:

[0140] S148-2 (22.03 g, 23.9 mmol) was added to a 1000 ml three-necked flask, and o-xylene (300 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (19 ml, 1.6 M, 27 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. In an ice-water bath, boron tribromide (6.58 g, 26.27 mmol) was extracted with a thick needle and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (6.17 g, 47.76 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (500 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (500 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 6 g of crude product was obtained by column chromatography. 3.64 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 17%. The molecular ion mass determined by mass spectrometry was 895.09 (theoretical value: 895.09).

[0141] Based on the same inventive concept, an embodiment of the present invention further provides an organic electronic light-emitting device comprising the compound prepared in the above synthesis embodiment. OLED is used as an organic electronic light-emitting device as an example of a device for illustration below, but it should be understood that the following detailed description is not a limitation of the present invention, and those skilled in the art can extend the following detailed description to other organic electronic light-emitting devices.

[0142] OLED includes a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0143] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0144] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0145] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0146] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0147] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-34 below; or any combination thereof.

[0148]

[0149]

[0150]

[0151] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-34, or one or more compounds of HI-1 to HI-3 described below; or one or more compounds of HT-1 to HT-34 can be doped with one or more compounds of HI-1 to HI-3 described below.

[0152]

[0153] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0154] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0155] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0156]

[0157] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an electron transport layer (ETL) of a single-layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0158] In a specific example, the electron transport layer material can be selected from but not limited to one or more of the following groups of ET-1 to ET-57.

[0159]

[0160]

[0161]

[0162]

[0163] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li and / or Ca.

[0164] Device Example 1:

[0165] In Example 1, the device structure is as follows:

[0166] ITO(150nm) / HI-2(10nm) / HT-2(40nm) / BFH-3:S1(30nm, 5%wt) / ET-46:ET-57(50 / 50,w / w)(25nm)) / LiF(0.5nm) / Al(150nm).

[0167] The preparation process of organic electroluminescent device is as follows:

[0168] A glass plate coated with a transparent conductive layer of ITO (thickness 150 nm) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0169] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5 Pa, HI-2 and HT-2 were vacuum evaporated on the above anode layer as hole injection layer and hole transport layer, respectively, with an evaporation rate of 0.1 nm / s and an evaporation film thickness of 10 nm and 40 nm, respectively;

[0170] "BFH-3: S1 (30nm, 5%wt)" is vacuum evaporated on the hole transport layer as the light-emitting layer of the organic electroluminescent device. The evaporation rate is 0.1nm / s and the total film thickness of the evaporation is 30nm; "5%wt" refers to the doping ratio of the dye, that is, the weight ratio of the main material to S1 is 95:5.

[0171] A mixture of ET-46:ET-57 (50 / 50, w / w) was vacuum-deposited on the light-emitting layer as the electron transport layer of the organic electroluminescent device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 25 nm;

[0172] 0.5 nm of LiF as an electron injection layer and 150 nm of Al as a cathode were vacuum-deposited on the electron transport layer.

[0173] Device Examples 2-6:

[0174] The preparation process of device examples 2-6 is the same as that of device example 1, except that the dye S1 is replaced by compounds S11, S37, S42, S64 and S73 of the present invention, respectively.

[0175] Comparative Example 1-2:

[0176] The preparation process of Comparative Example 1-2 is the same as that of Device Example 1, except that the dye S1 is replaced by compounds C1 and C2 in the prior art, respectively.

[0177]

[0178] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0179] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1 to 6 and Comparative Examples 1 to 2, as well as the device life, were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 1000 cd / m 2 The voltage at this time is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency.

[0180] Table 1

[0181]

[0182]

[0183] It can be seen from Table 1 above that, compared with the comparative examples prepared using the prior art compounds, the voltage of the embodiment device prepared using the compound of the present invention as the dye in the light-emitting layer is reduced, the efficiency of the device is improved, and the excellent OLED device performance is comprehensively shown. This is because the compound of the present invention introduces an electron-pushing group at a specific position, which is more compatible with the light-emitting main material, and the energy transfer efficiency is higher. At the same time, a rigid group is introduced, which improves the luminous efficiency of the material and increases the carrier mobility. It can be seen that the new organic material of the present invention is suitable as a light-emitting functional material for an organic electroluminescent device, and is an organic light-emitting functional material with good performance, and is expected to be promoted for commercial application. The practical value of the compound of the present invention is relatively large.

[0184] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A compound of the general formula, as shown in the following formula (1): In the general formula (1): Ar 1 is selected from substituted or unsubstituted phenyl; X is selected from CR 1 R 2 , O, S or SiR 3 R 4 ; R 1 , R 2 , R 3 and R 4 Each is independently selected from one of C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; R a , R b Each independently represents a monosubstituted to maximum permissible substituent, and is independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; R n represents a monosubstituted group, R n It is the structure shown in formula (Hy): In the formula (Hy): Ring A represents a single substitution to the maximum permissible substituent, and Ring A is fused to the benzene ring at at least one position among a, b and c, and Ring A is selected from a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group; R i represents monosubstituted to the maximum permissible substituent, selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; When the above groups have substituents, the substituents are selected from one or a combination of at least two of C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 monocyclic aromatic or condensed aromatic, C3-C30 monocyclic heteroaromatic or condensed heteroaromatic; And is not the following compound:

2. The compound of the general formula according to claim 1, as shown in the following formula (2-1), (2-2), (2-3) or (2-4): In formulas (2-1), (2-2), (2-3) and (2-4), R a , R b , R n and R 1 , R 2 , R 3 , R 4 and Ar 1 The definition of is the same as in the general formula (1).

3. The compound of the general formula according to claim 2, as shown in formula (2-3) or (2-4).

4. A compound of the general formula according to any one of claims 1 to 3, wherein Formula (Hy) is the following formula (Hy 1 ): Formula (Hy 1 ), the dotted line represents the site where the groups are fused, i.e., the formula (A-1) and the formula (Hy 1 ) are fused by site d with any of the three sites a, b or c; E 1 Selected from CR 5 R 6 NR 7 , O, S or SiR 8 R 9 One of the 5 , R 6 , R 7 , R 8 and R 9 Each is independently selected from one of C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; R h , R g and R i Each independently represents a single substituent to the maximum permissible substituent, and is independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R h , R g or R i can be independently connected with the corresponding R g , R h or R i The connected aromatic rings are fused to each other to form a substituted or unsubstituted C10-C30 aryl group or a substituted or unsubstituted C9-C30 heteroaryl group.

5. The compound of the general formula according to claim 4, wherein Formula (Hy 1 ) is selected from the following formula (Hy-1), (Hy-2), (Hy-3), (Hy-4) or (Hy-5):

6. A compound of the general formula according to any one of claims 1 to 4, wherein Formula (Hy) is selected from the following formula (Hy1), (Hy2), (Hy3) or (Hy4):

7. The compound of the general formula according to claim 1 is selected from the following specific structural compounds:

8. Use of the compound according to any one of claims 1 to 7 as a luminescent dye and / or sensitizer in a light-emitting layer in an organic electroluminescent device.

9. An organic electroluminescent device, comprising a first electrode, a second electrode and one or more organic functional layers inserted between the first electrode and the second electrode, characterized in that: The organic layer comprises at least one compound according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 9, wherein the organic functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is between the hole transport layer and the electron transport layer, wherein: The light-emitting layer contains the compound described in any one of claims 1-7.

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