Compound containing nitrogen heterocyclic structure and organic electroluminescent device

Abstract

The invention relates to a compound containing a nitrogen heterocyclic structure and an organic electroluminescent device. The deuterated or aryl substituted active sites of the compound improve the chemical stability, photoelectric stability and thermal stability of the compound, improve the stability of the device and further prolong the service life. According to the present invention, the P-type compound can form the good Premix material, the P-type compound has good P / N stability and mass production stability during the evaporation process, and the formed Premix material has more balanced carrier mobility, such that the efficiency of the device is substantially improved, and the service life of the device is substantially prolonged. The material provided by the invention has excellent solubility, can effectively solve the problems of hole blockage of a production line and difficult Mask cleaning, and can greatly reduce the preparation and recovery cost of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to a compound and an organic electroluminescence device. Background Art

[0002] Organic electroluminescence usually refers to an organic light-emitting diode (OLED) that uses electric current to drive an organic semiconductor film to emit light, thereby achieving the purpose of display.

[0003] The composition structure of an organic electroluminescent device includes a cathode, an anode, and an organic layer disposed therebetween. The organic layer structure of OLED devices currently used in the industry is usually a multilayer structure, for example, including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other film layers. For an OLED device including the above-mentioned film layers, when a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When holes and electrons meet, excitons are formed. When the excitons transfer energy to the doping material, light is emitted through the radiation transition of the doping material.

[0004] In existing OLED devices, due to the poor compatibility between green light hosts, energy cannot be efficiently transferred to doping materials, and the efficiency of conductive OLED devices has decreased. At the same time, since it has not been deuterated at the active sites and sites with high electron density of the material molecules, its chemical stability, thermal stability and photoelectric stability are poor, which in turn affects the life of the device. In addition, the P / N ratio of the current green light host will change greatly with the extension of the evaporation time, resulting in large fluctuations in device performance, poor stability and low yield.

[0005] The premix material formed by the combination of the N-type compound and the P-type compound of the present invention has good thermal stability, chemical stability and photoelectric stability because the active sites of their respective structures are deuterated. At the same time, the premix material formed by the compounds of the present invention has a balanced carrier mobility, further widens the exciton recombination area, and thus improves the life and efficiency of the device. Summary of the invention

[0006] The purpose of the present invention is to provide a compound containing a nitrogen heterocyclic structure and an organic electroluminescent device based on the prior art.

[0007] The purpose of the present invention can be achieved by the following measures: A compound containing a nitrogen heterocyclic structure, the structural formula of which is shown in Formula 1 below:

[0008] X is O, S or Se; Ar 1 and Ar 2 Each independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, pyridyl, pyrimidinyl, carbazolyl, dibenzofuranyl, dibenzothienyl, spirobifluorenyl, 9,9-dimethylfluorenyl, wherein Ar 1 and Ar 2 The substituent is selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C1-C10 cycloalkyl, C1-C10 deuterated cycloalkyl, C6-C30 aryl, C6-C30 deuterated aryl, and C5-C30 heteroaryl; L 1 -L 3 Each independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, wherein L 1 -L 3 The substituent is selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C6-C18 aryl, and C5-C20 heteroaryl; A 1 -A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, pyridyl, said A 1 -A 10 The substituents are selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, and cyclohexyl, and A 1 -A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl, pyridyl.

[0009] Preferably, its structural formula is shown in Formula 2-Formula 4 below:

[0010] X is O, S or Se; Ar 1 and Ar 2 is selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, pyridyl, carbazolyl, dibenzofuranyl, dibenzothienyl, spirobifluorenyl, 9,9-dimethylfluorenyl, wherein Ar 1 and Ar 2 The substituent is deuterium, fluorine, cyano, deuterated or undeuterated groups of the following groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, cyclohexyl or more; L 1and L 2 Each is independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, and pyridyl; A 1 -A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, pyridyl, said A 1 -A 10 The substituents are selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, and cyclohexyl, and A 1 -A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl, pyridyl; R 1 Each independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: one or more of phenyl, biphenyl, methyl, ethyl, tert-butyl; n is an integer from 0 to 4.

[0011] Preferably, X is O or S; Ar 1 and Ar 2 is selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, pyridyl, carbazolyl, dibenzofuranyl, dibenzothienyl, spirobifluorenyl, 9,9-dimethylfluorenyl, wherein Ar 1 and Ar 2 The substituent is deuterium, fluorine, cyano, deuterated or undeuterated groups of the following groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, cyclohexyl or more; L 1 and L 2 Each is independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A 1 -A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, said A 1 -A 10 The substituent is selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, and tert-butyl, and A 1 -A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R 1 Each independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: one or more of phenyl, methyl, tert-butyl; n is an integer from 0 to 4.

[0012] Preferably, X is O or S; Ar 1 and Ar 2 is selected from the following substituted or unsubstituted groups: phenyl, biphenyl, carbazolyl, dibenzofuranyl, dibenzthienyl, wherein Ar 1 and Ar 2 The substituent is deuterium, deuterated or undeuterated one or more of the following groups: phenyl, biphenyl, methyl, tert-butyl; L 1 and L 2 Each is independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A 1 -A 10 Each independently selected from the following groups: deuterium, substituted or unsubstituted: phenyl, biphenyl, naphthyl, wherein A 1 -A 10 The substituent is selected from one or more of deuterium, phenyl, deuterated phenyl, biphenyl, and deuterated biphenyl, and A 1 -A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R 1 Each independently selected from hydrogen, deuterium, deuterated or undeuterated groups: one or more of phenyl, methyl, tert-butyl; n is an integer from 0 to 4.

[0013] Further preferably, X is O or S; Ar 1 and Ar 2 Each independently selected from substituted or unsubstituted phenyl, biphenyl, said Ar 1 and Ar 2 The substituent is one or more of deuterium, phenyl, deuterated phenyl, methyl, and tert-butyl; L 1 and L 2 Each is independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A 1 -A 10 Each independently selected from the following groups: deuterium, substituted or unsubstituted: phenyl, biphenyl, naphthyl, wherein A 1 -A 10 The substituent is selected from one or more of deuterium, phenyl, and deuterated phenyl, and A 1 -A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R 1 are each independently selected from hydrogen or deuterium; n is an integer from 0 to 4.

[0014] In a preferred embodiment, the compound of the present invention is any one of the following compounds: .

[0015] An organic electroluminescent device comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode; wherein the organic layer contains the compound of the present invention.

[0016] Furthermore, the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; wherein the light-emitting layer contains the compound of the present invention.

[0017] Furthermore, the light-emitting layer further contains at least one of the following formula 5 or formula 6: in,

[0018] Ar 4 and Ar 5 Each independently selected from the following substituted or unsubstituted groups: C6-C30 aryl, C5-C30 heteroaryl, the Ar 4 and Ar 5The substituent is selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C1-C10 cycloalkyl, C1-C10 deuterated cycloalkyl, C6-C30 aryl, C6-C30 deuterated aryl, and C5-C30 heteroaryl; L 4 and L 5 Each independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, wherein L 4 and L 5 The substituent is selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C6-C18 aryl, and C5-C20 heteroaryl; R 2 -R 5 Each independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: one or more of phenyl, biphenyl, methyl, ethyl, tert-butyl; m and p are each independently an integer from 0 to 7; k is an integer from 0 to 6; g is an integer from 0 to 4.

[0019] Furthermore, the light-emitting layer contains a light-emitting host material, which is a mixture of the compound of the present invention and any one or more of compounds P-1 to P-88. Compounds P-1 to P-88 are as follows: .

[0020] An electronic display device containing the organic electroluminescent device of the present invention.

[0021] An OLED lighting device comprising the organic electroluminescent device of the present invention.

[0022] The room temperature described in the present invention is 25±5°C.

[0023] Beneficial effects of the present invention: The present invention designs a new type of organic electroluminescent material, which has the following excellent properties: 1. Deuteration or aromatic substitution of active sites improves the chemical stability, photoelectric stability and thermal stability of the compound, improves the stability of the device, and thus increases its lifespan.

[0024] 2. It can form a good Premix material with the P-type compound of the present invention, has good P / N stability and mass production stability during the evaporation process, and the formed Premix material has a more balanced carrier mobility, thereby greatly improving the efficiency and life of the device.

[0025] 3. The materials of the present invention have excellent solubility, which can effectively solve the problem of hole blocking in the production line and the difficulty in cleaning the mask, and at the same time can greatly reduce the preparation and recycling costs of the materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A schematic diagram of the structure of an organic electroluminescent device provided by the present invention; The numbers in the figure represent: 1-anode, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-light-emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, 9-cathode; Figure 2 It is the HPLC chart of compound 16 prepared in Example 1 of the present invention; Figure 3 It is the DSC spectrum of compound 16 prepared in Example 1 of the present invention. It can be seen from Figure 3 that the glass transition temperature Tg value of compound 16 is 135.26 °C; Figure 4 It is the TGA spectrum of compound 16 prepared in Example 1 of the present invention. It can be seen from Figure 4 that the thermal weight loss temperature Td value is 457.22 °C. Detailed implementation manners

[0027] The following further illustrates and describes the embodiments of various aspects. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. Instead, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure as defined by the appended claims.

[0028] As used herein, in "substituted" or "unsubstituted", the term "substituted" means that at least one hydrogen in the group is re-coordinated with deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). The term "unsubstituted" means that at least one hydrogen in the group is not re-coordinated with deuterium, a hydrocarbon group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). Examples of the hydrocarbon group or hydrocarbon derivative group may include, but are not limited to, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C30 alkylamino, C6-C30 arylamino, C6-C30 heteroarylamino, C6-C30 arylheteroarylamino, etc.

[0029] Deuterium in the present invention refers to a stable isotope form of hydrogen, also known as heavy hydrogen, and its element symbol is D.

[0030] As used herein, in "deuterated" or "undeuterated", the term "deuterated" means that at least one hydrogen in the group is re-coordinated with deuterium. The term "undeuterated" means that all hydrogens in the group are not re-coordinated with deuterium.

[0031] n is an integer from 0 to 4, which means n can be 0, 1, 2, 3, 4. Similarly, m and p are each independently integers from 0 to 7, which means m and p can each independently be 0, 1, 2, 3, 4, 5, 6, 7; k is an integer from 0 to 6, which means k can be 0, 1, 2, 3, 4, 5, 6; g is an integer from 0 to 4, which means g can be 0, 1, 2, 3, 4.

[0032] The aromatic group in the present invention refers to an all-carbon monocyclic or condensed polycyclic group of 6 to 30 carbon atoms, having a completely conjugated π electron system. Non-limiting examples of aromatic groups include phenyl, naphthyl, anthracenyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, triphenyl[1,12-bcd]furanyl, phenanthrenyl, and the like.

[0033] The “heteroaryl group” herein refers to a heteroaryl group obtained by replacing one or more C atoms in the structure of the “aryl group” with one or more heteroatoms (such as N, O or S).

[0034] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0035] Embodiment 1:

[0036]

[0037] The synthesis method of compound 16 is as follows:

[0038] 1-a (80 g, 0.227 mol, 1 eq) and deuterated benzene (382 g, 4.54 mol, 20 eq) were added to a 1L three-necked flask, and trifluoromethanesulfonic acid (238.5 g, 1.589 mol, 7 eq) was slowly added dropwise. After the addition was completed, the temperature was raised to 50 °C and stirred for 18-24 h. The reaction was stopped, and the reaction solution was slowly poured into 2000 ml of ice water, stirred for crystallization for 2 h, filtered, and the filter cake was rinsed with water and toluene. After the filter cake was dried, 100 g of 100-200 mesh silica gel sand was added, and 800 g of 100-200 mesh silica gel was loaded on the column, PE / DCM=100 / 1-50 / 1-20 / 1, the product point was collected, and it was concentrated to dryness under reduced pressure to obtain 68.9 g of off-white solid 1-b, with a yield of 84%.

[0039]

[0040] 1-b (68 g, 0.1883 mol, 1 eq), 1-c (24.1 g, 0.1977 mol, 1.05 eq), potassium carbonate (52 g, 0.3766 mol, 2 eq) and toluene / ethanol / water (700 ml + 350 ml + 210 ml) were added to a 2 L three-necked flask. 2Under protection, tetrakistriphenylphosphine palladium (4.35 g, 3.766 mmol, 0.02 eq) was added, the temperature was raised to reflux and stirred for reaction, and HPLC monitored 1-b ≤ 1%. The reaction was stopped, 200 ml of water was added, stirred and separated, the aqueous phase was extracted with DCM, the organic phases were combined, filtered through silica gel, the filtrate was concentrated to dryness under reduced pressure, 150 ml of ethanol was added, heated and stirred for 2 h, the temperature was lowered to room temperature for crystallization, filtered, and the filter cake was air-dried at 85 ° C to obtain 51 g of off-white solid 1-d, with a yield of 75.6%.

[0041]

[0042] 1-d (50 g, 0.14 mol, 1 eq), 1-e (54.2 g, 0.14 mol, 1 eq), sodium tert-butoxide (20.2 g, 0.21 mol, 1.5 eq) and toluene (500 ml) were added to a 1 L three-necked flask. 2 Under protection, Xphos Pd G4 (2.41 g, 2.8 mmol, 0.02 eq) was added, the temperature was raised to 100°C and stirred for reaction, and HPLC was monitored for 1-d≤1%. The reaction was stopped, and the mixture was filtered through silica gel while hot. The filtrate was concentrated to dryness under reduced pressure, 200 ml of toluene was added for hot dissolution, 200 ml of ethanol was added, the temperature was lowered and stirred for crystallization to room temperature, and the mixture was filtered. The filter cake was recrystallized from toluene / ethanol 4 times, and then recrystallized from pure toluene 2 times, and filtered. The filter cake was dried at 85°C with air blast to obtain 45.6 g of off-white solid compound 16 with a yield of 48.9%.

[0043] In a similar manner, the following compounds 1, 2, 6, 7, 13, 17, 20, 24, 26, 28, 29, 30, 35, 37, 48, 49, 50, 61, 62, 64, 65, 68, 69, 73, 74, 77, 78, 85, 97, 98, 101, 102, 109, 110, 113, 114, 120, 121, 122, 125, 126, 133, 134, 138, 139, 145, 146, 149, 150, 157, 169, 170, 173, 174, 181, 182, 183, 187, 188, 189, 197, 198, 201, 205, 210, 221, 222, 230 were obtained: Table 1-1

[0044] Table 1-2

[0045] Table 1-3

[0046] Table 1-4

[0047] Table 1-5

[0048] Table 1-6

[0049] Table 1-7

[0050] Table 1-8

[0051] Table 1-9

[0052] Table 1-10

[0053] Table 1-11

[0054] Table 1-12

[0055] Table 1-13

[0056] Table 1-14

[0057] Table 1-15

[0058] Table 1-16

[0059] Table 1-17

[0060] Table 1-18

[0061] Table 1-19

[0062] Table 1-20

[0063] Table 1-21

[0064] Table 1-22

[0065] The synthetic identification results of the compounds prepared above are shown in Table 2 below: Table 2 Compound FD-Quality Compound FD-Quality 1 m / z=665.21(C45H19D9N4S=665.26) 113 m / z=725.27(C51H23D9N4O=725.31) 2 m / z=665.22(C45H19D9N4S=665.26) 114 m / z=725.25(C51H23D9N4O=725.31) 6 m / z=665.21(C45H19D9N4S=665.26) 120 m / z=725.28(C51H23D9N4O=725.31) 7 m / z=665.24(C45H19D9N4S=665.26) 121 m / z=725.27(C51H23D9N4O=725.31) 13 m / z=715.25(C49H21D9N4S=715.28) 122 m / z=725.28(C51H23D9N4O=725.31) 16 m / z=665.22(C45H19D9N4S=665.26) 125 m / z=725.28(C51H23D9N4O=725.31) 17 m / z=665.24(C45H19D9N4S=665.26) 126 m / z=725.27(C51H23D9N4O=725.31) 20 m / z=665.21(C45H19D9N4S=665.26) 133 m / z=725.28(C51H23D9N4O=725.31) 24 m / z=670.25(C45H14D14N4S=670.29) 134 m / z=725.25(C51H23D9N4O= 725.31) 26 m / z=665.23(C45H19D9N4S=665.26) 137 m / z=725.26(C51H23D9N4O=725.31) 28 m / z=715.27(C49H21D9N4S=715.28) 138 m / z=725.26(C51H23D9N4O=725.31) 29 m / z=665.24(C45H19D9N4S=665.26) 139 m / z=725.28(C51H23D9N4O=725.31) 30 m / z=665.23(C45H19D9N4S=665.26) 145 m / z=725.27(C51H23D9N4O=725.31) 35 m / z=670.26(C45H14D14N4S=670.29) 146 m / z=725.29(C51H23D9N4O=725.31) 37 m / z=741.24(C51H23D9N4S=741.29) 149 m / z=725.27(C51H23D9N4O=725.31) 48 m / z=741.25(C51H23D9N4S=741.29) 150 m / z=725.28(C51H23D9N4O=725.31) 49 m / z=741.23(C51H23D9N4S=741.29) 157 m / z=725.28(C51H23D9N4O=725.31) 50 m / z=741.25(C51H23D9N4S=741.29) 169 m / z=725.24(C51H23D9N4O=725.31) 61 m / z=741.26(C51H23D9N4S=741.29) 170 m / z=725.26(C51H23D9N4O=725.31) 62 m / z=741.26(C51H23D9N4S=741.29) 173 m / z=725.25(C51H23D9N4O=725.31) 64 m / z=746.29(C51H18D14N4S=746.32) 174 m / z=725.24(C51H23D9N4O=725.31) 65 m / z=741.27(C51H23D9N4S=741.29) 181 m / z=649.25(C45H19D9N4O=649.28) 68 m / z=741.25(C51H23D9N4S=741.29) 182 m / z=649.23(C45H19D9N4O=649.28) 69 m / z=746.25(C51H18D14N4S=746.32) 183 m / z=654.25(C45H14D14N4O=654.31) 73 m / z=741.27(C51H23D9N4S=741.29) 187 m / z=649.24(C45H19D9N4O=649.28) 74 m / z=741..24(C51H23D9N4S=741.29) 188 m / z=699.27(C49H21D9N4O=699.30) 77 m / z=741.24(C51H23D9N4S=741.29) 189 m / z=649.21(C45H19D9N4O=649.28) 78 m / z=741.25(C51H23D9N4S=741.29) 197 m / z=649.25(C45H19D9N4O=649.28) 85 m / z=741.26(C51H23D9N4S=741.29) 198 m / z=649.24(C45H19D9N4O=649.28) 97 m / z=741.24(C51H23D9N4S=741.29) 201 m / z=699.25(C49H21D9N4O=699.30) 98 m / z=741.24(C51H23D9N4S=741.29) 205 m / z=699.24(C49H21D9N4O=699.30) 101 m / z=741.26(C51H23D9N4S=741.29) 210 m / z=649.22(C45H19D9N4O=649.28) 102 m / z=741.25(C51H23D9N4S=741.29) 221 m / z=649.24(C45H19D9N4O=649.28) 109 m / z=725.24(C51H23D9N4O=725.31) 222 m / z=649.23(C45H19D9N4O=649.28) 110 m / z=725.26(C51H23D9N4O=725.31) 230 m / z=654.28(C45H14D14N4O=654.31) Device performance test: Test compounds 1, 2, 6, 7, 13, 16, 17, 20, 24, 26, 28, 29, 30, 35, 37, 48, 49, 50, 61, 62, 64, 65, 68, 69, 73, 74, 77, 78, 85, 97, 98, 101, 102, 109, 110, 113, 114, 120, 121, 122, The thermal weight loss temperature Td and glass transition temperature Tg of 125, 126, 133, 134, 138, 139, 145, 146, 149, 150, 157, 169, 170, 173, 174, 181, 182, 183, 187, 188, 189, 197, 198, 201, 205, 210, 221, 222, 230 are shown in Table 3: Note: The thermal weight loss temperature Td is the temperature at which the weight loss is 5% in a nitrogen atmosphere. It is measured on a TGA N-1000 thermogravimetric analyzer with a nitrogen flow rate of 10 mL / min. The Tg (glass transition temperature) is measured by differential scanning calorimetry (DSC, Shinco DSC N-650) with a heating rate of 10°C / min.

[0066] Table 3: Test material (compound) Td (℃) Tg(℃) Test material (compound) Td (℃) Tg(℃) 1 466.51 148.36 113 440.91 147.29 2 458.69 137.45 114 446.28 136.25 6 445.23 138.20 120 451.39 148.98 7 469.21 140.57 121 470.41 126.34 13 472.55 135.67 122 465.32 130.58 16 457.22 135.26 125 445.68 126.81 17 429.74 145.31 126 462.50 132.74 20 444.39 153.20 133 453.98 143.11 24 437.26 143.54 134 455.35 141.62 26 438.37 137.48 137 462.64 139.48 28 449.30 146.32 138 438.58 128.79 29 462.71 148.08 139 439.71 137.56 30 452.36 136.89 145 459.67 135.25 35 468.17 141.59 146 460.64 139.87 37 462.85 151.48 149 449.42 142.60 48 458.86 134.61 150 453.88 134.72 49 443.92 127.85 157 472.30 127.45 50 438.08 133.87 169 463.97 130.65 61 448.69 136.54 170 466.83 142.38 62 459.10 141.86 173 457.09 137.50 64 463.28 139.47 174 448.34 135.18 65 452.84 136.79 181 458.40 142.67 68 459.33 140.87 182 450.92 126.15 69 468.12 128.45 183 466.20 135.67 73 452.57 130.70 187 459.24 148.78 74 463.82 134.55 188 471.31 145.62 77 446.16 141.46 189 466.82 139.50 78 438.94 143.92 197 468.29 134.22 85 459.25 138.73 198 459.41 145.15 97 451.14 137.63 201 462.87 135.87 98 442.65 129.88 205 448.05 137.28 101 448.16 132.81 210 452.94 140.85 102 452.97 145.97 221 469.86 139.01 109 437.68 136.42 222 475.62 147.49 110 432.56 144.25 230 453.62 138.27 As can be seen from Table 3 above, the compounds of the present invention have relatively high Td and Tg values, indicating that they have excellent thermal stability. Applying them to organic electroluminescent devices can effectively extend the service life of the organic electroluminescent devices and obtain better use effects.

[0067] Device performance test: Application Example 1:

[0068] ITO was used as the reflective layer anode substrate material, and water, acetone, N 2 Plasma treatment of its surface; On top of the ITO anode substrate, 10 nm of HT-1 doped with 5% NDP-9 was deposited to form a hole injection layer (HIL); A hole transport layer (HTL) was formed by evaporating 100 nm of HT-1 on the hole injection layer (HIL); Vacuum evaporate GP on the hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 10 nm; Compound 16 prepared in Example 1 of the present invention and compound P-1 were co-evaporated at a ratio of 5:5 as the main luminescent material, and GD-1 was evaporated as a doping material (the amount of GD-1 was 8% of the total weight of compound 16 and P-1) on the second hole transport layer (GPL) to form a luminescent layer with a thickness of 20 nm; HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm; ET-1 and LiQ were co-evaporated onto the hole blocking layer (HBL) at a ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm; Magnesium (Mg) and silver (Ag) were mixed in a ratio of 9:1 and evaporated onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm. Thereafter, silver (Ag) is evaporated onto the electron injection layer to form a cathode with a thickness of 100 nm, and a DNTPD with a thickness of 50 nm is deposited on the cathode sealing layer. In addition, the cathode surface is sealed with a UV curable adhesive and a sealing film (seal cap) containing a dehumidifier to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere. Thus, an organic electroluminescent device is prepared.

[0069]

[0070] Application Example 2-70 The compounds 1, 2, 6, 7, 13, 17, 20, 24, 26, 28, 29, 30, 35, 37, 48, 49, 56, 61, 62, 64, 65, 68, 69, 73, 74, 77, 78, 85, 97, 98, 101, 102, 109, 110, 113, 114, 120, 121, 122, 125, 126, 133 in Examples 2-70 of the present invention were used respectively. , 134, 138, 139, 145, 146, 149, 150, 157, 169, 170, 173, 174, 181, 182, 183, 187, 188, 189, 197, 198, 201, 205, 210, 221, 222, and 230 replace compound 16 in application example 1, and the other parts are consistent with application example 1, and the organic electroluminescent devices of application examples 2-70 are prepared based on this.

[0071] Comparative Examples 1-3 The difference between Control Examples 1-3 and Application Example 1 is that Compounds D1 and D2 in CN117751111A are used respectively, and Compound D3 in CN106661041A replaces Compound 16 in Application Example 1, and the rest is the same as Application Example 1.

[0072] The organic electroluminescent devices prepared in Application Examples 1-70 and Comparative Examples 1-3 were tested respectively, and the test results are shown in Table 4.

[0073] Table 4 Experimental Group Luminescent host material <![CDATA[Current density (mA / cm 2 ).]]> Voltage (V) Luminous efficiency (Cd / A) Emitting color Comparative Example 1 D1+P-1 10 3.59 166.3 green Comparative Example 2 D2+P-1 10 3.56 159.7 green Comparative Example 3 D3+P-1 10 3.70 161.5 green Application Example 1 16+P-1 10 3.30 217.3 green Application Example 2 1+P-1 10 3.36 208.5 green Application Example 3 2+P-1 10 3.35 197.3 green Application Example 4 6+P-1 10 3.38 195.7 green Application Example 5 7+P-1 10 3.36 192.1 green Application Example 6 13+P-1 10 3.43 202.6 green Application Example 7 17+P-1 10 3.38 192.4 green Application Example 8 20+P-1 10 3.42 205.0 green Application Example 9 24+P-1 10 3.36 197.4 green Application Example 10 26+P-1 10 3.31 185.4 green Application Example 11 28+P-1 10 3.42 208.1 green Application Example 12 29+P-1 10 3.37 198.0 green Application Example 13 30+P-1 10 3.31 193.7 green Application Example 14 35+P-1 10 3.37 196.5 green Application Example 15 37+P-1 10 3.31 193.4 green Application Example 16 48+P-1 10 3.40 203.8 green Application Example 17 49+P-1 10 3.39 207.5 green Application Example 18 50+P-1 10 3.32 196.3 green Application Example 19 61+P-1 10 3.37 198.0 green Application Example 20 62+P-1 10 3.35 195.9 green Application Example 21 61+P-1 10 3.34 194.6 green Application Example 22 65+P-1 10 3.32 196.8 green Application Example 23 68+P-1 10 3.39 201.3 green Application Example 24 69+P-1 10 3.38 196.7 green Application Example 25 73+P-1 10 3.41 210.5 green Application Example 26 74+P-1 10 3.38 196.5 green Application Example 27 77+P-1 10 3.39 204.6 green Application Example 28 78+P-1 10 3.36 193.2 green Application Example 29 85+P-1 10 3.42 198.3 green Application Example 30 97+P-1 10 3.40 208.6 green Application Example 31 98+P-1 10 3.37 196.2 green Application Example 32 101+P-1 10 3.42 198.3 green Application Example 33 102+P-1 10 3.32 192.6 green Application Example 34 109+P-1 10 3.35 199.3 green Application Example 35 110+P-1 10 3.38 190.5 green Application Example 36 113+P-1 10 3.35 188.3 green Application Example 37 114+P-1 10 3.40 196.3 green Application Example 38 120+P-1 10 3.43 197.2 green Application Example 39 121+P-1 10 3.35 192.7 green Application Example 40 122+P-1 10 3.39 201.8 green Application Example 41 125+P-1 10 3.45 203.6 green Application Example 42 126+P-1 10 3.37 186.3 green Application Example 43 133+P-1 10 3.37 194.3 green Application Example 44 134+P-1 10 3.41 198.5 green Application Example 45 137+P-1 10 3.46 203.8 green Application Example 46 138+P-1 10 3.34 187.3 green Application Example 47 139+P-1 10 3.38 196.7 green Application Example 48 145+P-1 10 3.37 192.5 green Application Example 49 146+P-1 10 3.43 203.6 green Application Example 50 149+P-1 10 3.41 199.6 green Application Example 51 150+P-1 10 3.38 195.3 green Application Example 52 157+P-1 10 3.35 186.7 green Application Example 53 169+P-1 10 3.36 185.5 green Application Example 54 170+P-1 10 3.34 183.0 green Application Example 55 173+P-1 10 3.38 192.6 green Application Example 56 174+P-1 10 3.41 198.3 green Application Example 57 181+P-1 10 3.36 197.6 green Application Example 58 182+P-1 10 3.41 201.0 green Application Example 59 183+P-1 10 3.35 192.4 green Application Example 60 187+P-1 10 3.36 197.3 green Application Example 61 188+P-1 10 3.41 197.2 green Application Example 62 189+P-1 10 3.44 203.4 green Application Example 63 197+P-1 10 3.37 196.0 green Application Example 64 198+P-1 10 3.40 194.3 green Application Example 65 201+P-1 10 3.39 196.7 green Application Example 66 205+P-1 10 3.46 199.4 green Application Example 67 210+P-1 10 3.38 190.8 green Application Example 68 221+P-1 10 3.41 197.6 green Application Example 69 222+P-1 10 3.44 198.9 green Application Example 70 230+P-1 10 3.38 192.4 green It can be seen from Table 4 above that the application of the compound of the present invention in an organic electroluminescent device as a main material of a light-emitting layer can improve the luminous efficiency of the organic electroluminescent device to a certain extent, reduce the starting voltage, and relatively reduce power consumption.

[0074] The organic electroluminescent devices prepared in the control examples 1-6 and the application examples 1-15, 36-40 were tested for luminescence lifetime to obtain the luminescence lifetime T97% data (the time when the luminescence brightness decreases to 97% of the initial brightness). The test equipment was a TEO luminescent device lifetime test system. The results are shown in Table 5: Table 5 Experimental Group <![CDATA[Current density (mA / cm 2 )]]> T97% Comparative Example 1 10 98% Comparative Example 2 10 100% Comparative Example 3 10 90% Application Example 1 10 159% Application Example 2 10 146% Application Example 3 10 147% Application Example 4 10 132% Application Example 5 10 142% Application Example 6 10 153% Application Example 7 10 140% Application Example 8 10 147% Application Example 9 10 142% Application Example 10 10 138% Application Example 11 10 141% Application Example 12 10 152% Application Example 13 10 147% Application Example 14 10 146% Application Example 15 10 142% Application Example 36 10 138% Application Example 37 10 146% Application Example 38 10 149% Application Example 39 10 144% Application Example 40 10 146% It can be seen from Table 5 above that when the compound of the present invention is used as the main material of the light-emitting layer and applied to an organic electroluminescent device, the service life of the prepared organic electroluminescent device is greatly improved, so it has a very broad application prospect.

Claims

1. A compound containing a nitrogen heterocyclic structure, characterized in that: Its structural formula is shown in Formula 1 below: ； X is O, S or Se; Ar1 and Ar2 are each independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, pyridyl, pyrimidyl, carbazolyl, dibenzofuranyl, dibenzothienyl, spirobifluorenyl, 9,9-dimethylfluorenyl, and the substituents of Ar1 and Ar2 are selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C1-C10 cycloalkyl, C1-C10 deuterated cycloalkyl, C6-C30 aryl, C6-C30 deuterated aryl, and C5-C30 heteroaryl; L1-L3 are each independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group, and the substituents of L1-L3 are selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C6-C18 aryl, and C5-C20 heteroaryl; A1-A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, pyridyl, said A1-A 10 The substituent is selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, and cyclohexyl, and A1-A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl, pyridyl.

2. The compound as claimed in claim 1, characterized in that Its structural formula is shown in Formula 2-Formula 4 below: ； X is O, S or Se; Ar1 and Ar2 are selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, pyridyl, carbazolyl, dibenzofuranyl, dibenzothienyl, spirobifluorenyl, 9,9-dimethylfluorenyl, and the substituents of Ar1 and Ar2 are deuterium, fluorine, cyano, deuterated or undeuterated groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, cyclohexyl or one or more thereof; L1 and L2 are each independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, and pyridyl; A1-A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, pyridyl, said A1-A 10 The substituent is selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, and cyclohexyl, and A1-A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl, pyridyl; R1 is independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, or one or more thereof; n is an integer from 0 to 4.

3. The compound according to claim 1 or 2, characterized in that X is O or S; Ar1 and Ar2 are selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, pyridyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, spirobifluorenyl, 9,9-dimethylfluorenyl, and the substituents of Ar1 and Ar2 are deuterium, fluorine, cyano, deuterated or undeuterated groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, cyclopentyl, cyclohexyl or one or more thereof; L1 and L2 are each independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A1-A 10 Each independently selected from deuterium, fluorine, cyano, substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, said A1-A 10 The substituent is selected from one or more of deuterium, fluorine, cyano, phenyl, biphenyl, methyl, and tert-butyl, and A1-A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R1 is independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: phenyl, methyl, tert-butyl or more; n is an integer from 0 to 4.

4. The compound according to claim 1 or 2, characterized in that X is O or S; Ar1 and Ar2 are selected from the following substituted or unsubstituted groups: phenyl, biphenyl, carbazolyl, dibenzofuranyl, dibenthienyl, and the substituents of Ar1 and Ar2 are deuterated, deuterated or undeuterated groups: one or more of phenyl, biphenyl, methyl, and tert-butyl; L1 and L2 are each independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A1-A 10 Each independently selected from the following groups: deuterium, substituted or unsubstituted: phenyl, biphenyl, naphthyl, said A1-A 10 The substituent is selected from one or more of deuterium, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, and A1-A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R1 is independently selected from hydrogen, deuterium, deuterated or undeuterated groups: one or more of phenyl, methyl, tert-butyl; n is an integer from 0 to 4.

5. The compound according to claim 1 or 2, characterized in that X is O or S; Ar1 and Ar2 are each independently selected from substituted or unsubstituted phenyl and biphenyl groups, and the substituents of Ar1 and Ar2 are one or more of deuterium, phenyl, deuterated phenyl, methyl and tert-butyl groups; L1 and L2 are each independently selected from a single bond, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl; A1-A 10 Each independently selected from the following groups: deuterium, substituted or unsubstituted: phenyl, biphenyl, naphthyl, said A1-A 10 The substituent is selected from one or more of deuterium, phenyl, and deuterated phenyl, and A1-A 10 At least one of the following groups is substituted or unsubstituted: phenyl, biphenyl, naphthyl; R1 is each independently selected from hydrogen or deuterium; n is an integer from 0 to 4.

6. The compound according to claim 1, characterized in that The compound is any one of the following compounds: 。 7. An organic electroluminescent device, characterized in that: The invention comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode; the organic layer contains the compound according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; and the light-emitting layer contains the compound according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, characterized in that: The light-emitting layer further contains at least one of the following formula 5 or formula 6: in, ; Ar4 and Ar5 are each independently selected from the following substituted or unsubstituted groups: C6-C30 aryl, C5-C30 heteroaryl, and the substituents of Ar4 and Ar5 are selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C1-C10 deuterated alkyl, C1-C10 cycloalkyl, C1-C10 deuterated cycloalkyl, C6-C30 aryl, C6-C30 deuterated aryl, and C5-C30 heteroaryl; L4 and L5 are each independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group, and the substituents of L4 and L5 are selected from one or more of deuterium, fluorine, cyano, C1-C10 alkyl, C6-C18 aryl, and C5-C20 heteroaryl; R2-R5 are each independently selected from hydrogen, deuterium, fluorine, cyano, deuterated or undeuterated groups: phenyl, biphenyl, methyl, ethyl, tert-butyl, or one or more thereof; m and p are each independently an integer from 0 to 7; k is an integer from 0 to 6; g is an integer from 0 to 4.

10. The organic electroluminescent device according to claim 8 or 9, characterized in that: The light-emitting layer contains a light-emitting host material, and the light-emitting host material is a mixture of any one or more of the compound according to any one of claims 1 to 6 and compounds P-1 to P-88. Compounds P-1 to P-88 are as follows: 。 11. An electronic display device, characterized in that: Contains the organic electroluminescent device as claimed in claim 7.

Images