Polycyclic compounds and organic electroluminescent devices comprising the same

Abstract

This invention discloses a polycyclic compound with the general structural formula shown in Formula I. This polycyclic compound has good stability and large molecular steric hindrance, which can greatly reduce the concentration quenching effect and facilitate energy conduction. When this polycyclic compound is used as a dopant in the organic light-emitting layer of an organic electroluminescent device, the dopant can effectively improve the external quantum efficiency of the organic electroluminescent device and extend its lifetime, overcoming the shortcomings of the prior art.

Description

Technical Field

[0001] This invention belongs to the field of OLED technology, specifically including a polycyclic compound and an organic electroluminescent device containing the same. Background Technology

[0002] Organic light-emitting diodes (OLEDs), due to their advantages such as self-illumination, high contrast, thinness, light weight, wide viewing angle, and fast response speed, have become one of the key development directions in the display industry. OLED devices typically consist of an ITO transparent anode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a metal cathode. When a certain voltage is applied to the two electrodes, the anode injects holes into the hole injection layer, and the cathode injects electrons into the electron injection layer. Electrons and holes migrate from the anode and cathode to the central light-emitting layer, where they meet to form excitons. When these excitons radiate and de-excite, their energy is released in the form of photons, thus emitting light.

[0003] In recent years, the commercial application of OLED products has been mainly concentrated in displays for televisions, mobile phones, etc. For small-sized OLED screens, device efficiency and lifespan are crucial performance indicators. The organic light-emitting layer consists of two substances: a host material and dopants. Displays for televisions, mobile phones, etc., achieve full color using red, green, and blue colors; therefore, the organic light-emitting layer is composed of red host / dopant, green host / dopant, and blue host / dopant, respectively. Currently, red or green light-emitting materials are usually phosphorescent materials, while blue light-emitting materials are mostly fluorescent materials. Quantum theory spin statistical calculations show that the formation ratio of singlet and triplet excitons is 1:3, meaning singlet excitons account for 25% and triplet excitons account for 75%. Therefore, theoretically, the maximum quantum efficiency of organic electroluminescence prepared using blue fluorescent light-emitting materials is only 25%.

[0004] In full-color display research, blue fluorescent luminescent materials possess advantages such as good stability and pure light color. However, on the one hand, the maximum quantum efficiency of organic electroluminescent devices (OLEDs) fabricated using fluorescent materials limits the improvement of the efficiency of blue fluorescent materials; on the other hand, due to the short wavelength and high energy of blue light, the stability of the luminescent material during the luminescence process severely affects the lifetime of blue fluorescent devices; furthermore, blue luminescent materials often employ large-planar aryl compounds, which makes it easy for luminescent molecules to aggregate, leading to concentration quenching and significantly reducing the efficiency and lifetime of organic electroluminescent devices. Therefore, there is an urgent need to develop a blue luminescent material with high efficiency and long lifetime. Summary of the Invention

[0005] In view of this, the present invention provides a polycyclic compound and an organic electroluminescent device containing the same. The polycyclic compound has good stability and large molecular steric hindrance, which can avoid concentration quenching caused by molecular aggregation and is beneficial to energy conduction. When the polycyclic compound is used as a blue dopant in the organic light-emitting layer of the organic electroluminescent device, the blue dopant can effectively improve the external quantum efficiency of the organic electroluminescent device and extend the lifetime of the organic electroluminescent device, overcoming the defects of the prior art.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: The first aspect of the present invention provides a polycyclic compound, the general structural formula of which is shown in Formula I:

[0007]

[0008] in,

[0009] X is either B or P = O;

[0010] The ring M and ring N may be the same or different, and each is independently selected from any one or any combination of several of the following: aryl group with 5 to 60 substituted or unsubstituted carbon atoms, heteroaryl group with 4 to 60 substituted or unsubstituted carbon atoms, fused-ring aryl group with 10 to 60 substituted or unsubstituted carbon atoms, fused-ring heteroaryl group with 8 to 60 substituted or unsubstituted carbon atoms, and cycloalkyl group with 3 to 30 substituted or unsubstituted carbon atoms.

[0011] Y1 is selected from any one of O, S, Se or NR2;

[0012] The Y2 is selected from any one of O, S, Se or N;

[0013] R1 and R2 are selected from hydrogen, deuterium, cyano, nitro, hydroxyl, alkyl groups with 1 to 30 substituted or unsubstituted carbon atoms, alkoxy groups with 1 to 30 substituted or unsubstituted carbon atoms, alkylthio groups with 1 to 30 substituted or unsubstituted carbon atoms, trialkylsilyl groups with 3 to 12 substituted or unsubstituted carbon atoms, triarylsilyl groups with 18 to 24 substituted or unsubstituted carbon atoms, alkenyl groups with 2 to 30 substituted or unsubstituted carbon atoms, cycloalkyl groups with 3 to 30 substituted or unsubstituted carbon atoms, and alkyl groups with 3 to 30 substituted or unsubstituted carbon atoms. The R1 group comprises any one or a combination of several of the following: aryl group with 6 to 60 carbon atoms, heteroaryl group with 5 to 60 carbon atoms (substituted or unsubstituted), fused-ring aryl group with 6 to 60 carbon atoms (substituted or unsubstituted), fused-ring heteroaryl group with 5 to 60 carbon atoms (substituted or unsubstituted), amino group with substituted or unsubstituted carbazole group with substituted or unsubstituted ether group with substituted or unsubstituted ether group; R1 can be fused with the connected benzene ring to form an aromatic ring or heteroaromatic ring with 9 to 30 carbon atoms; R2 can be synthesized into a ring by a linker group or a single bond and a ring M bond.

[0014] Z1 and Z2 are each independently selected from Any one of O, S or single bond, and Z1 and Z2 are not both single bonds;

[0015] The R3 to R 13 Each is independently selected from any one or any combination of hydrogen, deuterium, alkyl groups having 1 to 30 carbon atoms (substituted or unsubstituted), cycloalkyl groups having 3 to 30 carbon atoms (substituted or unsubstituted), aryl groups having 6 to 60 carbon atoms (substituted or unsubstituted), heteroaryl groups having 5 to 60 carbon atoms (substituted or unsubstituted), fused-ring aryl groups having 6 to 60 carbon atoms (substituted or unsubstituted), and fused-ring heteroaryl groups having 5 to 60 carbon atoms (substituted or unsubstituted).

[0016] When the rings M, N, R1 to R 13 When any of the substituents are present in rings M, N, R1 to R, 13The substituents may be one or more, and each may be independently selected from deuterium, cyano, nitro, hydroxyl, alkyl with 1 to 10 carbon atoms, alkoxy with 1 to 15 carbon atoms, alkylthio with 1 to 15 carbon atoms, trialkylsilyl with 3 to 12 carbon atoms, triarylsilyl with 18 to 24 carbon atoms, cycloalkyl with 3 to 15 carbon atoms, alkenyl with 2 to 10 carbon atoms, aryloxy with 6 to 12 carbon atoms, etc. The substituents are any one of the following: arylthiol group with 6 to 12 carbon atoms, alkylsulfonyl group with 6 to 12 carbon atoms, aryl group with 6 to 30 carbon atoms, heteroaryl group with 5 to 30 carbon atoms, fused-ring aryl group with 10 to 30 carbon atoms, fused-ring heteroaryl group with 9 to 30 carbon atoms, or diarylamine group, wherein two or more substituents can be bonded to each other through a linking group or a single bond to form an aliphatic ring, aromatic ring, heteroaromatic ring, fused ring, or fused heterocyclic ring;

[0017] Any hydrogen atom on the ring structure of the polycyclic compound shown in Formula I can be independently replaced by deuterium, cyano, alkyl, cycloalkyl, aryl, heteroaryl, or arylamino.

[0018] In conjunction with the first aspect, rings M and N are each independently selected from...

[0019] Or any one of the cycloalkyl groups having 3 to 15 carbon atoms;

[0020] In the cyclic M or cyclic N structure, any non-adjacent carbon can be independently replaced by nitrogen, and any hydrogen can be independently replaced by deuterium, cyano, straight-chain alkyl, branched alkyl, cycloalkyl, aryl, heteroaryl, or arylamino.

[0021] In conjunction with the first aspect, the amino group is selected from one of alkylamino groups having 1 to 10 substituted or unsubstituted carbon atoms, arylamino groups having 6 to 20 substituted or unsubstituted carbon atoms, heteroarylamino groups having 5 to 20 substituted or unsubstituted carbon atoms, and aralkylamino groups having 6 to 20 substituted or unsubstituted carbon atoms.

[0022] In conjunction with the first aspect, R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, alkyl groups having 1 to 10 carbon atoms (substituted or unsubstituted), Any one or any combination of them;

[0023] The R 14 R 15Each of the R groups is independently selected from any one or any combination of several of the following: alkyl groups having 1 to 10 carbon atoms (substituted or unsubstituted), cycloalkyl groups having 3 to 15 carbon atoms (substituted or unsubstituted), alkenyl groups having 2 to 10 carbon atoms (substituted or unsubstituted), and aryl groups having 6 to 20 carbon atoms (substituted or unsubstituted). 14 R 15 They can be bonded together by linking groups or single bonds to form aliphatic rings, aromatic rings or heteroaromatic rings, and any one of the hydrogens in R1 can be independently replaced by deuterium, straight-chain alkyl, branched alkyl, cycloalkyl or phenyl.

[0024] In conjunction with the first aspect, R2 is selected from alkyl groups having 1 to 10 carbon atoms, whether substituted or unsubstituted.

[0025] Any one or any combination of them;

[0026] The R 14 R 15 Each of the R2 groups is independently selected from any one or any combination of several of the following: alkyl groups having 1 to 10 carbon atoms (substituted or unsubstituted), cycloalkyl groups having 3 to 15 carbon atoms (substituted or unsubstituted), alkenyl groups having 2 to 10 carbon atoms (substituted or unsubstituted), and aryl groups having 6 to 20 carbon atoms (substituted or unsubstituted). Each hydrogen atom in R2 can be independently substituted by deuterium, straight-chain alkyl, branched alkyl, cycloalkyl, or phenyl. R2 can be connected to ring M to form any one of the following: substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0027] In conjunction with the first aspect, the compound represented by Formula I is selected from any one of the structures represented by Formulas I-1 to I-5 below:

[0028]

[0029] Any hydrogen atom on the ring structure of the polycyclic compounds shown in Formulas I-1 to I-5 can be independently replaced by deuterium, cyano, alkyl, cycloalkyl, aryl, heteroaryl, or arylamino.

[0030] In conjunction with the first aspect, the compounds represented by Formulas I-1 to I-4 are any one of the following compounds:

[0031]

[0032]

[0033] Any hydrogen atom on the ring structure of the polycyclic compounds shown in Formulas I-1-1 to I-4-3 can be independently replaced by deuterium, cyano, alkyl, cycloalkyl, aryl, heteroaryl, or arylamino.

[0034] In conjunction with the first aspect, the compound represented by Formula I is selected from any one of the following compounds:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] A second aspect of the present invention provides the application of the above-mentioned polycyclic compounds in the field of organic electroluminescence.

[0048] A third aspect of the present invention provides an organic electroluminescent device, comprising an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate; wherein the light-emitting layer comprises a host material and a dopant material, and the dopant material comprises one or more polycyclic compounds as described in any one of claims 1-8.

[0049] The beneficial effects of this invention are as follows:

[0050] The polycyclic compound provided by this invention contains a large molecular weight aryl spirocyclic structure, which greatly expands the molecular size. The unique twisted structure of the spirocyclic structure can increase the steric hindrance between molecules, avoiding concentration quenching caused by molecular aggregation. In addition, the aryl spirocyclic ring in the polycyclic compound provided by this invention is a multi-component spirocyclic ring, which has a relatively stable structure. Furthermore, heteroatoms such as nitrogen, oxygen, silicon, or sulfur can be introduced into the multi-component spirocyclic ring. These heteroatoms can enhance the spin coupling between triplet and singlet states, which is beneficial for the conversion of triplet excitons into fluorescent singlet excitons, thereby improving the efficiency and lifetime of organic light-emitting devices (OLEDs). When the polycyclic compound provided by this invention is used as a blue dopant in the organic light-emitting layer of OLEDs, the blue dopant exhibits good stability and large molecular steric hindrance, effectively avoiding concentration quenching caused by molecular aggregation, improving the external quantum efficiency of OLEDs, and extending the lifetime of OLEDs, overcoming the shortcomings of existing technologies. The polycyclic compound provided by this invention is suitable for blue host / dopant systems in the blue series of AM-OLEDs and OLEDs. Attached image description:

[0051] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0052] Figure 1 This is a schematic diagram of the structure of an organic electroluminescent device containing the polycyclic compound of the present invention;

[0053] Figure description: 1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-light-emitting auxiliary layer, 6-light-emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode. Detailed Implementation

[0054] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further clarifies the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention. The embodiments and comparative examples in this specification are provided to provide a more complete explanation of the specification to those skilled in the art. Various modifications can be made based on the embodiments and comparative examples in this specification, and the scope of protection of the present invention should not be limited to the embodiments and comparative examples detailed below.

[0055] The compounds of this invention are applicable to light-emitting elements, display panels, and electronic devices, particularly organic electroluminescent devices. The electronic devices of this invention are devices comprising a layer of at least one organic compound, and may also comprise layers of inorganic materials or layers formed entirely of inorganic materials. Preferred electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic dye-sensitized solar cells (O-DSSCs), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasma emitting devices. Organic electroluminescent devices (OLEDs) are particularly preferred.

[0056] The aromatic amine compounds of the present invention are prepared by using the Buchwald-Hartwig coupling reaction, the Suzuki coupling reaction or the Heck coupling reaction as representative reactions.

[0057] To better understand the content of this invention, the polycyclic compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to embodiments. Various chemical reactions can be applied to the synthesis method of the compound according to one embodiment of this invention. However, it should be noted that the synthesis method of the compound according to one embodiment of this invention is not limited to the synthesis method described below. Unless otherwise stated, subsequent synthesis is carried out in an anhydrous solvent under a protective gas atmosphere. Solvents and reagents can be purchased from conventional reagent suppliers.

[0058] intermediate synthesis

[0059]

[0060] The general formula for intermediate synthesis is as above. The target intermediate can be obtained through two common Buchwald-Hartwig coupling synthesis methods.

[0061] Intermediate Example 1

[0062] Specific examples are as follows:

[0063]

[0064] Y-1 (20.52 g; 100 mmol), Y-2 (21.5 g; 90 mmol), and sodium tert-butoxide (10.5 g, 110 mmol) were added to toluene (500 mL). Under nitrogen protection, palladium dibenzylacetone (2.74 g, 3.0 mmol) and SPhos (2.46 g, 6 mmol) were introduced. The reaction mixture was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. The final product, Sub1, was 29.48 g (yield: 90%), MS (m / z) (M+): 364.

[0065]

[0066] Y-3 (37.34 g; 100 mmol), Y-4 (30.51 g; 90 mmol), and sodium tert-butoxide (10.5 g, 110 mmol) were added to toluene (500 mL). Under nitrogen protection, palladium dibenzylacetone (2.74 g, 3.0 mmol) and SPhos (2.46 g, 6 mmol) were introduced. The reaction mixture was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. The final product, Sub4, was obtained as 44.75 g (yield: 85%), MS (m / z) (M+): 585.

[0067]

[0068] Sub1 (3.64 g; 10 mmol), Sub2 (2.71 g; 9 mmol), and sodium tert-butoxide (1.05 g, 11 mmol) were then added to toluene (50 mL). Under nitrogen protection, palladium dibenzylacetone (274.28 mg, 0.30 mmol) and tri-tert-butylphosphine (121.2 mg, 0.6 mmol) were introduced. The reaction mixture was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. The final product, Sub3, was obtained as 4.57 g (yield: 87%), MS (m / z) (M+): 584.

[0069] Sub3 (5.84 g; 10 mmol), Sub4 (3.60 g; 10 mmol), and sodium tert-butoxide (1.05 g, 11 mmol) were then added to toluene (100 ml). Under nitrogen protection, palladium dibenzylacetone (274.28 mg, 0.30 mmol) and tri-tert-butylphosphine (121.2 mg, 0.6 mmol) were introduced. The reaction mixture was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. The final product, A-3, was obtained: 7.17 g (yield: 66%), MS (m / z) (M+): 1087.

[0070] After obtaining A-3 through the above process, other intermediates can be obtained by using a similar method to A-3.

[0071] Compound Synthesis

[0072] Compound Example 1

[0073]

[0074] A-3 (10.87 g; 10 mmol) was added to tert-butylbenzene (125 ml), and then the mixture was cooled to 0 °C under nitrogen protection. 12.4 ml (21 mmol) of a 1.7 M tert-butyllithium pentane solution was added, and the mixture was heated to 60 °C and stirred for 2 hours. The mixture was then cooled to 0 °C, and 2.0 ml (21 mmol) of boron tribromide was added and stirred for 0.5 hours. The mixture was then cooled to 0 °C, and 3.65 ml (21 mmol) of N,N-diisopropylethylamine was added. The mixture was heated to 60 °C and stirred for 2 hours. After cooling to room temperature, the mixture was quenched with ice water and separated. The organic phase was filtered, and water was removed using anhydrous magnesium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by recrystallization from dichloromethane and n-heptane. The final product was F-3: 0.71 g (yield: 7%), MS (m / z) (M+): 1016.

[0075] Compound Example 2

[0076]

[0077] The method was the same as in Compound Example 1, except that A-19 (11.28 g; 10 mmol) was replaced with A-3, and the final product F-19 was obtained: 0.95 g (yield: 9%), MS (m / z) (M+): 1057.

[0078] Compound Example 3

[0079]

[0080] The method was the same as in Compound Example 1, except that A-22 (11.73 g; 10 mmol) was replaced with A-3, and the final product was F-22: 0.77 g (yield: 7%), MS (m / z) (M+): 1102.

[0081] Compound Example 4

[0082]

[0083] The method was the same as in Compound Example 1, except that A-31 (12.35 g; 10 mmol) was replaced with A-3, and the final product F-31 was obtained: 1.05 g (yield: 9%), MS (m / z) (M+): 1163.

[0084] Compound Example 5

[0085]

[0086] The method was the same as in Compound Example 1, except that A-32 (11.18 g; 10 mmol) was replaced with A-3, and the final product F-32 was obtained: 1.47 g (yield: 14%), MS (m / z) (M+): 1047.

[0087] Compound Example 6

[0088]

[0089] The method was the same as in Compound Example 1, except that A-74 (10.34 g; 10 mmol) was replaced with A-3, and the final product F-74 was obtained: 1.06 g (yield: 11%), MS (m / z) (M+): 963.

[0090] Compound Example 7

[0091]

[0092] The method was the same as in Compound Example 1, except that A-75 (9.63 g; 10 mmol) was replaced with A-3, and the final product C-75 was obtained: 0.98 g (yield: 11%), MS (m / z) (M+): 892.

[0093] Compound Example 8

[0094]

[0095] The method was the same as in Compound Example 1, except that A-95 (9.87 g; 10 mmol) was replaced with A-3, and the final product was F-95: 0.73 g (yield: 8%), MS (m / z) (M+): 916.

[0096] Compound Example 9

[0097]

[0098] The method was the same as in Compound Example 1, except that A-96 (11.74 g; 10 mmol) was replaced with A-3, and the final product F-96 was obtained: 1.43 g (yield: 13%), MS (m / z) (M+): 1103.

[0099] Compound Example 10

[0100]

[0101] The method was the same as in Compound Example 1, except that A-143 (12.94 g; 10 mmol) was replaced with A-3, and the final product was F-143: 1.1 g (yield: 9%), MS (m / z) (M+): 1222.

[0102] Compound Example 11

[0103]

[0104] The method was the same as in Compound Example 1, except that A-150 (11.8 g; 10 mmol) was replaced with A-3, and the final product was F-150: 1 g (yield: 9%), MS (m / z) (M+): 1109.

[0105] Compound Example 12

[0106]

[0107] The method was the same as in Compound Example 1, except that A-161 (10.7 g; 10 mmol) was replaced with A-3, and the final product was F-161: 1 g (yield: 10%), MS (m / z) (M+): 999.

[0108] Compound Example 13

[0109]

[0110] The method was the same as in Compound Example 1, except that A-181 (9.42 g; 10 mmol) was replaced with A-3, and the final product was F-181: 0.87 g (yield: 10%), MS (m / z) (M+): 871.

[0111] Compound Example 14

[0112]

[0113] The method was the same as in Compound Example 1, except that A-196 (10.41 g; 10 mmol) was replaced with A-3, and the final product was F-196: 0.58 g (yield: 6%), MS (m / z) (M+): 970.

[0114] Compound Example 15

[0115]

[0116] The method was the same as in Compound Example 1, except that A-197 (11.58 g; 10 mmol) was replaced with A-3, and the final product was F-197: 0.98 g (yield: 9%), MS (m / z) (M+): 1087.

[0117] Compound Example 16

[0118]

[0119] The method was the same as in Compound Example 1, except that A-241 (10.05 g; 10 mmol) was replaced with A-3, and the final product was F-241: 0.93 g (yield: 10%), MS (m / z) (M+): 934.

[0120] Compound Example 17

[0121]

[0122] The method was the same as in Compound Example 1, except that A-253 (9.31 g; 10 mmol) was replaced with A-3, and the final product was F-253: 0.86 g (yield: 10%), MS (m / z) (M+): 860.

[0123] Compound Example 18

[0124]

[0125] The method was the same as in Compound Example 1, except that A-255 (9.8 g; 10 mmol) was replaced with A-3, and the final product was F-255: 1.27 g (yield: 14%), MS (m / z) (M+): 909.

[0126] Compound Example 19

[0127]

[0128] The method was the same as in Compound Example 1, except that A-256 (9.16 g; 10 mmol) was replaced with A-3, and the final product was F-256: 1.1 g (yield: 13%), MS (m / z) (M+): 845.

[0129] Compound Example 20

[0130]

[0131] The method was the same as in Compound Example 1, except that A-259 (10.47 g; 10 mmol) was replaced with A-3, and the final product was F-259: 0.98 g (yield: 10%), MS (m / z) (M+): 976.

[0132] Comparative Example 1: This comparative example provides a compound BD1 that was tested during the research process. Its specific structural formula is as follows:

[0133]

[0134] Comparative Example 2

[0135] This comparative example provides a compound BD2 that was tested during the research process, and its specific structural formula is as follows:

[0136]

[0137] Comparative Example 3 of Compounds

[0138] This comparative example provides a compound BD3 that was tested during the research process, and its specific structural formula is as follows:

[0139]

[0140] Device Examples

[0141] The organic electroluminescent device provided by this invention has the following structural schematic diagram: Figure 1 As shown, it includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting auxiliary layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9, which are sequentially disposed on a substrate 1.

[0142] Furthermore, the hole transport region includes a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer; the electron transport region includes an electron transport layer and an electron injection layer.

[0143] Furthermore, the light-emitting layer is composed of a host material and doped materials, and the host material of the light-emitting layer can be composed of one molecular material or multiple molecular materials.

[0144] The polycyclic compound described in this invention can be used as one or more layers of the above-mentioned organic electroluminescent device, preferably as a doping material for the light-emitting layer of the device.

[0145] In this embodiment, the anode uses a commonly used anode material in the art, such as ITO, Ag, or their multilayer structures. The hole injection layer uses a commonly used hole injection material in the art, and is doped with F4TCNQ, HATCN, NDP-9, etc. The hole transport layer uses a commonly used hole transport material in the art. The light-emitting layer uses a commonly used light-emitting material in the art, for example, it can be composed of a host material and a dopant material, where the dopant material is the polycyclic compound provided by this invention. The electron transport layer uses a commonly used electron transport material in the art. The electron injection layer uses a commonly used electron injection material in the art, such as Liq, LiF, Yb, etc. The cathode uses a commonly used material in the art, such as metallic Al, Ag, or metal mixtures (Ag-doped Mg, Ag-doped Ca, etc.).

[0146] The electrode fabrication method and the deposition method of each functional layer in this embodiment are conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, and will not be described in detail here. Only some process details and testing methods in the fabrication process are supplemented as follows:

[0147] Device Example 1

[0148] This embodiment provides a blue organic light-emitting diode (OLED), the fabrication method of which is as follows: First, a hole injection layer is formed on an ITO layer (anode) formed on a substrate by vacuum deposition of HTL and p-dopant (HTL to p-dopant mass ratio of 98:2) with a thickness of 10 nm; on the hole injection layer, a hole transport layer is formed by vacuum deposition of HTL with a thickness of 120 nm; on the hole transport layer, a B2O3 layer is formed by vacuum deposition with a thickness of 5 nm. A light-emitting auxiliary layer is formed by depositing a prime matrix on the light-emitting auxiliary layer. A 20 nm thick mixture of BH and F-3 is then vacuum-deposited to form a light-emitting layer, with BH as the host and F-3 as the dopant, and a host-to-dopant mass ratio of 98:2. Next, a 5 nm thick hole-blocking layer (HBL) is vacuum-deposited on the light-emitting layer. An electron transport layer is formed by vacuum-depositing a 30 nm thick mixture of ET and Liq (ET to Liq mass ratio of 1:1). Then, an electron injection layer is formed by depositing LiF on the electron transport layer with a thickness of 0.2 nm. Finally, an electron cathode is formed by depositing aluminum (Al) on the electron injection layer with a thickness of 150 nm, thus fabricating a blue organic light-emitting device.

[0149] Except for the dopant in the light-emitting layer, the molecular structures of the other layers are as follows:

[0150]

[0151] Device Examples 2-20

[0152] The method is the same as in Device Example 1, except that F-3 is replaced with compounds from Compound Examples 2 to 20.

[0153] Device Comparison Examples 1-3

[0154] The method is the same as in Device Example 1, except that F-3 is replaced with compounds BD1, BD2, and BD3 in Compound Comparative Examples 1-3.

[0155] Performance evaluation of organic electroluminescent devices

[0156] Example of effect

[0157] The organic electroluminescent devices provided in Device Examples 1-20 and Comparative Examples 1-3 were tested using standard methods. For this purpose, J = 10 mA / cm² was used. 2 The driving voltage, luminance, electroluminescent current efficiency (in cd / A), and external quantum efficiency (EQE, in percentage) of the organic electroluminescent device were determined at a given current density, calculated as a function of luminescence density from the current / voltage / luminescence density characteristic line (IVL characteristic line) exhibiting Lambertian emission characteristics, and the emission spectrum. The lifetime LT was defined as the time after which, when operating at a constant current J, the luminance decreased from the initial luminance L0 to a specific proportion L1; J = 50 mA / cm². 2 The statement L1 = 90% refers to a value of 50 mA / cm. 2 When operating below the threshold, the luminous intensity decreases to 90% of its initial value L0 after time LT. Similarly, J = 20 mA / cm² 2 L1 = 80% means that at 20 mA / cm 2 When operating below the threshold, the luminous intensity drops to 80% of its initial value L0 after time LT.

[0158] The data for various OLED devices are summarized in Table 1. The parameters of the examples and comparative examples are compared to demonstrate the performance data of the various OLED devices.

[0159] The testing instruments and methods used to perform performance testing on the OLED devices of the above embodiments and comparative examples are as follows:

[0160] Brightness was tested using a PhotoResearch PR-635 spectral scanner;

[0161] Current density and turn-on voltage: tested using a Keithley 2400 digital source meter;

[0162] Life test: The LT-96ch life test device was used.

[0163] The performance test results of the above devices are listed in Table 1.

[0164] Table 1 Performance test results of blue light devices

[0165]

[0166] As shown in Table 1 above, the device performance test results indicate that when the polycyclic compound provided by this invention is used as a blue dopant in the organic light-emitting layer of an organic electroluminescent device, the efficiency and lifetime of the organic electroluminescent device provided by this invention are significantly improved compared with the comparative example, and the driving voltage does not increase significantly. This is because the polycyclic compound provided by this invention has good stability and large molecular steric hindrance, which can effectively avoid concentration quenching caused by molecular aggregation. Furthermore, the multi-component spirocyclic rings in the polycyclic compound provided by this invention can introduce heteroatoms such as nitrogen, oxygen, silicon, or sulfur. These heteroatoms can enhance the spin coupling between triplet and singlet states, which is beneficial for the transformation of triplet excitons into fluorescent singlet excitons, thereby improving the efficiency and lifetime of the organic electroluminescent device. This demonstrates that the polycyclic compound provided by this invention is a high-performance blue dopant material that can meet the performance requirements of blue organic electroluminescent devices and has practical value.

[0167] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A polycyclic compound, characterized by, The general structural formula of the polycyclic compound is any one of the compounds shown below: in, X is B; Y1 is NR2; Y2 is N; R1 is selected from hydrogen, deuterium, cyano, nitro, hydroxyl, and alkyl groups having 1 to 6 carbon atoms, whether substituted or unsubstituted. The R2 is selected from hydrogen, deuterium, cyano, nitro, hydroxyl, alkyl with 1 to 6 carbon atoms (substituted or unsubstituted), aryl with 6 to 12 carbon atoms (substituted or unsubstituted), and fused-ring heteroaryl with 5 to 12 carbon atoms (substituted or unsubstituted). each of Z1, Z2 is independently selected from , O or a single bond, and Z1, Z2 are not simultaneously a single bond, and in the formula I-1-1, Z1 is selected from , O, a single bond, Z2 is selected from O or a single bond; The R3, R4, R 11 R 12 R 13 Each is independently selected from hydrogen, deuterium, alkyl groups having 1 to 6 carbon atoms (substituted or unsubstituted), cycloalkyl groups having 3 to 12 carbon atoms (substituted or unsubstituted), and aryl groups having 6 to 12 carbon atoms (substituted or unsubstituted). When R1, R2, R3, R4, R 11 R 12 R 13 When any of the components contains a substituent, the substituent may be one or more, and each is independently selected from deuterium, cyano, nitro, hydroxyl, and alkyl groups having 1 to 6 carbon atoms.

2. The polycyclic compound of claim 1, wherein The compound represented by Formula I is selected from any one of the following compounds:

3. Use of a polycyclic compound according to any one of claims 1 to 2 in an organic electroluminescence device, characterized in that, The organic electroluminescent device includes an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate; wherein the light-emitting layer includes a host material and a dopant material, and the dopant material includes one or more polycyclic compounds as described in any one of claims 1-2.

4. An organic electroluminescent device, characterized by comprising It includes an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate; wherein the light-emitting layer includes a host material and a dopant material, and the dopant material includes one or more polycyclic compounds as described in any one of claims 1-2.

Images