Pyrene organic compounds, mixtures, compositions and organic electronic devices

Abstract

The present application relates to a kind of pyrene organic compounds, mixture, composition and organic electronic device.The pyrene organic compound has the structure shown in formula (I), has fluorescent emission with short wavelength of luminescence wavelength, shows deep blue fluorescent emission.The pyrene organic compound described in the present application is used as guest light-emitting material, in the light-emitting layer of organic electronic device, can effectively improve the luminous efficiency and lifetime of organic electronic device.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and in particular to a pyrene-based organic compound, mixture, composition, and organic electronic device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the diversity of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

[0003] Organic electroluminescence (OEC) refers to the phenomenon of converting electrical energy into light energy using organic materials. OEC devices typically have a positive electrode, a negative electrode, and an organic layer between them. To improve the efficiency and lifetime of OEC devices, the organic layer has a multi-layered structure, with each layer containing a different organic material. Specifically, it may include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In such OEC devices, applying a voltage between the two electrodes injects holes into the organic layer from the positive electrode and electrons into the organic layer from the negative electrode. When the injected holes and electrons meet, excitons are formed, and when these excitons transition back to the ground state, they emit light. Such OEC devices possess characteristics such as self-illumination, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

[0004] To improve the luminous efficiency of organic light-emitting diodes (OLEDs), various fluorescent and phosphorescent luminescent material systems have been developed. However, the development of excellent blue light-emitting materials, whether fluorescent or phosphorescent, remains a significant challenge. Generally speaking, OLEDs using blue fluorescent materials have higher reliability. Nevertheless, most current blue fluorescent materials have excessively broad emission spectra and poor color purity, which are detrimental to high-end displays. Furthermore, the synthesis of these materials is complex, hindering large-scale mass production. Additionally, the stability of OLEDs using these blue fluorescent materials needs further improvement. Therefore, developing blue fluorescent materials with narrow-band emission spectra and good stability is beneficial for obtaining longer-life and more efficient blue light-emitting devices, as well as for improving the color gamut, thereby enhancing display performance.

[0005] Existing blue organic light-emitting diodes (OLEDs) employ a host-guest doped structure for their emitting layer. Current host materials for blue light emission are anthracene-based fused-ring derivatives, such as those described in patents CN1914293B, CN102448945B, and US2015287928A1. However, these compounds suffer from insufficient luminous efficiency and brightness, as well as poor device lifespan. Existing guest compounds for blue light emission include arylvinylamine compounds (WO04 / 013073A1, WO04 / 016575A1, WO04 / 018587A1). However, these compounds exhibit poor thermal stability and are prone to decomposition, leading to poor device lifespan, which is currently the most significant drawback in the industry. Furthermore, these compounds have poor color purity, making it difficult to achieve deep blue light emission. In addition, patents such as US7233019B2 and KR20060006760A disclose organic electroluminescent elements using pyrene compounds with arylamine substituents. However, because the color purity of blue light is low, it is difficult to achieve deep blue light emission, which poses a problem for full-color displays that reproduce natural colors.

[0006] Therefore, further improvements are still needed in materials, especially luminescent compounds, particularly blue luminescent compounds. The goal is to enable blue luminescent materials to emit a deep blue light, be thermally stable, exhibit good efficiency and lifetime in organic electroluminescent devices, be easily reproducible in device fabrication and operation, and have simple material synthesis. Summary of the Invention

[0007] Based on this, the purpose of the present invention is to provide a pyrene-based organic compound, mixture, composition, and organic electronic device to improve the efficiency and lifespan of the device.

[0008] The technical solution is as follows:

[0009] A pyrene-based organic compound having a structure as shown in general formula (I):

[0010]

[0011] in:

[0012] Each of Ar1-Ar4 is independently selected from an aromatic group with 6 to 60 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 60 substituted or unsubstituted ring atoms.

[0013] And at least one of Ar1-Ar4 is selected from equation (II):

[0014]

[0015] Each time W appears, it is independently selected from O, S, CR. 12 R 13 or NR14 ;

[0016] * indicates a connection point;

[0017] R 10 R 11 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, or cyclic alkyl groups having 3 to 20 carbon atoms;

[0018] L is selected from a single bond, or an aromatic group with 6 to 30 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 30 substituted or unsubstituted ring atoms;

[0019] R1-R9, R 12 -R 14 Each occurrence is independently selected from -H, -D, or straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain thioalkoxy groups having 1 to 20 carbon atoms, or branched alkyl groups having 3 to 20 carbon atoms, branched alkoxy groups having 3 to 20 carbon atoms, branched thioalkoxy groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, cyclic alkoxy groups having 3 to 20 carbon atoms, or cyclic thioalkoxy groups having 3 to 20 carbon atoms, or silyl groups, or ketone groups having 1 to 20 carbon atoms, or groups having 2 to 20 carbon atoms. Alkoxycarbonyl, or aryloxycarbonyl having 7 to 20 carbon atoms, cyano, carbamoyl, halocarbamoyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, or alkenyl having 2 to 20 carbon atoms, or an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, or a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, or an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, or a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups;

[0020] n is selected from 0, 1, 2, 3, or 4.

[0021] The present invention also provides a mixture comprising the above-mentioned pyrene-based organic compounds and organic functional materials, wherein the organic functional materials are selected from at least one of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials, and organic dyes.

[0022] The present invention also provides a composition comprising the above-described pyrene organic compounds, or mixtures thereof, and at least one organic solvent.

[0023] The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode, wherein the organic functional layers comprise the above-described pyrene-based organic compounds, or mixtures thereof, or are prepared from the above-described compositions.

[0024] The present invention has the following beneficial effects:

[0025] The pyrene-based organic compounds provided by this invention exhibit deep blue fluorescence emission. Using these pyrene-based organic compounds as guest luminescent materials, in conjunction with the host material, in the luminescent layer of organic electronic devices can effectively improve the luminous efficiency and lifespan of the devices. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of an OLED structure according to an embodiment of the present invention;

[0027] Figure 2 This is the mass spectrum of compound 3;

[0028] Figure 3 This is the mass spectrum of compound 8. Detailed Implementation

[0029] The present invention will be further described in detail below with reference to specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0031] In this invention, the term "comprising" means "including but not limited to". The term "a plurality of" means "two or more". Various embodiments of the invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single digits within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the range referred to. Any integer between 0 and 8 includes 0, 1, 2, 3, 4, 5, 6, 7, and 8.

[0032] In this invention, the terms "composition" and "printing ink" or "ink" have the same meaning and can be used interchangeably.

[0033] In this invention, aromatic groups, aromatic families, and aromatic ring systems have the same meaning and can be used interchangeably.

[0034] In this invention, heteroaromatic groups, heteroaromatic families, and heteroaromatic ring systems have the same meaning and can be used interchangeably.

[0035] In this invention, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0036] In this invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents R, wherein R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-20 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halocarbamoyl, etc. Formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted with substituents acceptable in the art; it is understood that R' and R" in -NR'R" are independently selected from, but not limited to: H, deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, and heteroaromatic group containing 5-20 ring atoms.

[0037] In this invention, halogen refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0038] In this invention, "ring atom number" refers to the number of atoms in the ring-forming atoms of a structural compound (e.g., monocyclic compound, fused ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0039] In this application, "alkyl" can mean straight-chain, branched, and / or cyclic alkyl. The number of carbon atoms in an alkyl group can be 1-20, 1-10, or 1-6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl 2-Butyloctyl, 2-Hexyloctyl, 3,7-Dimethyloctyl, Cyclooctyl, Nonyl, Decyl, Adamantyl, 2-Ethyldecyl, 2-Butyldecyl, 2-Hexyldecyl, 2-Ocyldecyl, Undecyl, Dodecyl, 2-Ethyldodecyl, 2-Butyldodecyl, 2-Hexyldodecyl, 2-Ocyldodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, 2-Ethylhexadecyl, 2-Butylhexadecyl, 2-Hexylhexadecyl, 2-Ocylhexadecyl, Heptadecanyl, Octadecanyl, Nonadecanyl, Eicosyl, etc.

[0040] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic rings, at least one is an aromatic ring system. For example, "aryl with 6 to 40 substituted or unsubstituted ring atoms" means an aryl containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl with 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl with 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl with 6 to 14 ring atoms, and optionally further substituted on the aryl group; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, fluoranthyl, phenanthrene, benzo[a]phenanthrene, dinaphthylphenyl, tetraphenyl, pyrene, benzo[a]pyrene, acenaphthyl, fluorene, and their derivatives. Understandably, multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N, or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, and diaryl ether systems should also be included in the definition of aryl.

[0041] "Heteroaryl or heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, "a heteroaryl group with 5 to 40 substituted or unsubstituted ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a heteroaryl group with 6 to 30 substituted or unsubstituted ring atoms, more preferably a heteroaryl group with 6 to 18 substituted or unsubstituted ring atoms, and particularly preferably a heteroaryl group with 6 to 14 substituted or unsubstituted ring atoms. The heteroaryl group may optionally be further substituted, and suitable examples include, but are not limited to, triazine, pyridinyl, pyrimidinyl, imidazole, etc. Furanyl, thiophenyl, benzofuranyl, benzothiophenyl, indolyl, carbazoyl, pyrroloimidazoyl, pyrrolopyrryl, thiophenolopyrryl, thiophenolothiophenyl, furanopyrryl, furanofuranyl, thiophenolofuranyl, benzoisoxazolyl, benzoisothiazoyl, benzoimidazoyl, quinolinyl, isoquinolinyl, o-diazonyl, quinoxalinyl, phenanthridine, primidyl, quinazolinyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazoyl and their derivatives.

[0042] The term "alkoxy" refers to a group having an -O-alkyl group, i.e., an alkyl group as defined above that is attached to the parent nucleus via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0043] In this invention, the abbreviations for substituents are: n-n-, sec-sec-, i-iso-, t-tert-, o-ortho-, m-me-, p-para-, Me-methyl, Et-ethyl, Pr-propyl, Bu-butyl, Am-pentyl, Hx-hexyl, Cy-cyclohexyl.

[0044] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0045] In this invention, when no fusion site is specified in the group, it means that any fusionable site in the group is selected as the fusion site, preferably two or more sites in the adjacent position of the group are fusion sites.

[0046] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... Six Rs on the benzene ring 1 They can be the same as or different from each other.

[0047] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be attached to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0048] In this invention, cyclic alkyl or cycloalkyl has the same meaning and can be used interchangeably.

[0049] The statement that two adjacent substituents can optionally connect to form a ring is also intended to be understood as referring to two substituents bonded to the same carbon atom connecting to each other by chemical bonds to form a ring; preferably forming a 5-membered or 6-membered ring, such as cyclohexane or adamantane.

[0050] In the embodiments of this invention, the energy level structure of organic materials, specifically the triplet energy levels ET, HOMO, and LUMO, plays a crucial role. The determination of these energy levels is described below.

[0051] HOMO and LUMO energy levels can be measured using the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0052] The triplet energy level ET1 of organic materials can be measured by low-temperature time-resolved emission spectroscopy or obtained by quantum simulation calculations (such as by Time-dependent DFT), such as using commercial software Gaussian 09W (Gaussian Inc.). For specific simulation methods, please refer to WO2011141110 or as described below in the examples.

[0053] It should be noted that the absolute values ​​of HOMO, LUMO, and ET1 depend on the measurement or calculation method used. Even for the same method, different evaluation methods, such as those at the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement and evaluation methods. In the description of the embodiments of this invention, the values ​​of HOMO, LUMO, and ET1 are based on Time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0054] In this invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) as the third highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital energy level, (LUMO+2) as the third lowest occupied orbital energy level, and so on.

[0055] The purpose of this invention is to provide a pyrene-based organic compound and its application to improve the color purity and luminous efficiency of blue light emitters.

[0056] The technical solution is as follows:

[0057] A pyrene-based organic compound having a structure as shown in general formula (I):

[0058]

[0059] in:

[0060] Each of Ar1-Ar4 is independently selected from an aromatic group with 6 to 60 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 60 substituted or unsubstituted ring atoms.

[0061] And at least one of Ar1-Ar4 is selected from equation (II):

[0062]

[0063] Each time W appears, it is independently selected from O, S, and CR. 12 R 13 or NR 14 ;

[0064] * indicates a connection point;

[0065] R 10 R 11 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, or cyclic alkyl groups having 3 to 20 carbon atoms;

[0066] L is selected from a single bond, or an aromatic group with 6 to 30 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 30 substituted or unsubstituted ring atoms;

[0067] R1-R9, R 12 -R 14 Each occurrence is independently selected from -H, -D, or straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain thioalkoxy groups having 1 to 20 carbon atoms, or branched alkyl groups having 3 to 20 carbon atoms, branched alkoxy groups having 3 to 20 carbon atoms, branched thioalkoxy groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, cyclic alkoxy groups having 3 to 20 carbon atoms, or cyclic thioalkoxy groups having 3 to 20 carbon atoms, or silyl groups, or ketone groups having 1 to 20 carbon atoms, or groups having 2 to 20 carbon atoms. Alkoxycarbonyl, or aryloxycarbonyl having 7 to 20 carbon atoms, cyano, carbamoyl, halocarbamoyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, or alkenyl having 2 to 20 carbon atoms, or an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, or a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, or an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, or a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups;

[0068] n is selected from 0, 1, 2, 3, or 4.

[0069] In one embodiment, R1-R9, R 12 -R 14Each occurrence is independently selected from -H, -D, or straight-chain alkyl groups having 1 to 10 carbon atoms, straight-chain alkoxy groups having 1 to 10 carbon atoms, straight-chain thioalkoxy groups having 1 to 10 carbon atoms, or branched alkyl groups having 3 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms, branched thioalkoxy groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, cyclic alkoxy groups having 3 to 10 carbon atoms, or cyclic thioalkoxy groups having 3 to 10 carbon atoms, or silyl groups, or ketone groups having 1 to 10 carbon atoms, or groups having 2 to 10 carbon atoms. Alkoxycarbonyl, or aryloxycarbonyl having 7 to 10 carbon atoms, cyano, carbamoyl, halocarbamoyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, or alkenyl having 2 to 20 carbon atoms, or an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, or a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms, or an aryloxy group having 6 to 30 substituted or unsubstituted ring atoms, or a heteroaryloxy group having 5 to 30 substituted or unsubstituted ring atoms, or a combination of these groups.

[0070] In one embodiment, R3 and R7, each time they appear, are independently selected from -H, -D, or a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms; further, R3 and R7, each time they appear, are independently selected from -H, -D, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1 -Methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, or 2-(2-methyl)butyl. Further, R3 and R7 are selected from the same group. Even further, R1-R2, R4-R6, and R8-R9 are selected from -H or -D.

[0071] In one embodiment, R 12 -R 13 Each occurrence is independently selected from -H, -D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a phenyl group; further, R 12-R 13 Each occurrence is independently selected from -H, -D, or methyl, ethyl, isopropyl, or phenyl.

[0072] In one embodiment, R 14 Each occurrence is independently selected from -H, -D, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic group having 6 to 10 substituted or unsubstituted ring atoms, or a heteroaromatic group having 5 to 13 substituted or unsubstituted ring atoms; further, R 14 Each occurrence is independently selected from -H, -D, or methyl, ethyl, or isopropyl, or tert-butyl, or phenyl, or pyridyl, or pyrimidinyl, or triazine, or naphthyl, or biphenyl, or terphenyl.

[0073] In one embodiment, the pyrene-based organic compound is selected from formula (III):

[0074]

[0075] in:

[0076] Each occurrence of Ar2-Ar4 is independently selected from an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, or a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms.

[0077] In one embodiment, the substituent R in "substituted or unsubstituted" as described in this application can be monosubstituted or polysubstituted, preferably derived from a deuterium atom, cyano, isocyano, nitro, halogen atom, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 6 to 20 ring atoms, or a combination of the above groups.

[0078] In one embodiment, Ar2-Ar4 in formula (III) are each independently selected from any one of (A-1)-(A-6):

[0079]

[0080] in:

[0081] X is selected from N or CR 101 ;

[0082] Y is selected from O, S, S=O, SO2, NR 102 PR 102 CR 102 R 103 or SiR 102 R 103 ;

[0083] R 101 -R 103 Each occurrence is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain thioalkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, branched or cyclic alkoxy groups having 3 to 20 carbon atoms, branched or cyclic thioalkoxy groups having 3 to 20 carbon atoms, silyl groups, ketone groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, and aromatic groups having 7 to 20 carbon atoms. Oxycarbonyl, cyano, carbamoyl, halocarbamoyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF3, -Cl, -Br, -F, or alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 60 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 60 ring atoms, substituted or unsubstituted aryloxy groups having 5 to 60 ring atoms, substituted or unsubstituted heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups;

[0084] Adjacent R 101 Interconnected to form a loop or not; adjacent R 102 and R 103 They may be connected to form a ring or not.

[0085] When X is a connection site, X is selected from C.

[0086] In one embodiment, the pyrene-based organic compound is selected from formula (IV):

[0087]

[0088] Preferably, Ar2-Ar3 in formula (IV) are each independently selected from any one of (A-1)-(A-6).

[0089] In one embodiment, L is selected from a single bond, or an aromatic group having 6 to 10 substituted or unsubstituted ring atoms, or a heteroaromatic group having 6 to 10 substituted or unsubstituted ring atoms; further, L is selected from a single bond, or phenyl, or biphenyl, or terphenyl, or naphthyl; in one embodiment, when L appears multiple times, it is selected from the same group.

[0090] In one embodiment, formula (IV) is selected from any of the structures (V-1)-(V-4):

[0091]

[0092] In one embodiment, R 10 R11 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms; further, R 10 R 11 Each occurrence is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, and cyclohexyl.

[0093] In one embodiment, R 10 R 11 Each occurrence is selected from the same functional group.

[0094] In one embodiment, Ar2-Ar4 in formula (III) and Ar2-Ar3 in formula (IV) are each independently selected from the following groups:

[0095]

[0096] Where: R 101 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms;

[0097] m1 is selected from 0, 1, 2, 3, 4 or 5; m2 is selected from 0, 1, 2, 3 or 4; m3 is selected from 0, 1, 2 or 3; m4 is selected from 0, 1 or 2.

[0098] * indicates a connection point.

[0099] Furthermore, R 101 Each occurrence is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, and cyclohexyl.

[0100] In one embodiment, (A-3) is selected from the following structures:

[0101]

[0102] Furthermore, (A-3) is selected from the following structures Where: Y and R 101The definition is as described above. The possible reason is that it enhances molecular conjugation, resulting in better overall molecular planarity, which in turn improves the device's chromatic aberration, making it more biased towards deep blue light.

[0103] In one embodiment, Selected from

[0104] In one embodiment, in formulas (IV) and (V-1)-(V-4): Ar2 and Ar3 are the same group.

[0105] The pyrene-based organic compounds according to the present invention are preferably, but not limited to, the following structures, and the hydrogen on the ring can be further substituted:

[0106] Wherein, t-Bu is tert-butyl, tAm is tert-pentyl, Ph is phenyl, iPr is isopropyl, and Et is ethyl.

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] The pyrene-based organic compounds according to the present invention can be used as organic functional materials in organic electronic devices, particularly OLED devices. The organic functional materials can be selected from at least one of hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), emitters, host materials, and organic dyes.

[0117] In one embodiment, the pyrene-based organic compound according to the present invention is used in the light-emitting layer, preferably as a guest material in the light-emitting layer.

[0118] This invention further relates to a mixture comprising at least one pyrene-based organic compound as described above and at least one other organic functional material selected from hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), luminescent materials, host materials, and organic dyes. Detailed descriptions of various organic functional materials are available in WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated herein by reference.

[0119] In one embodiment, the other organic functional material is selected from the host material; further, the other organic functional material is selected from the blue light host material.

[0120] The present invention also relates to a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent; wherein the at least one organic solvent is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or borate esters or phosphate esters, or mixtures of two or more solvents.

[0121] In a preferred embodiment, a composition according to the invention is characterized in that the at least one organic solvent is selected from aromatic or heteroaromatic solvents.

[0122] Examples of solvents suitable for use in this invention, based on aromatic or heteroaromatic solvents, include, but are not limited to: p-diisopropylbenzene, pentanylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-Isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furanoate, ethyl 2-furanoate, etc.

[0123] Examples of aromatic ketone solvents suitable for this invention include, but are not limited to: 1-tetrahydronaphthone, 2-tetrahydronaphthone, 2-(phenylepoxy)tetrahydronaphthone, 6-(methoxy)tetrahydronaphthone, acetophenone, phenylacetone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylphenylacetone, 3-methylphenylacetone, 2-methylphenylacetone, etc.

[0124] Examples of aromatic ether solvents suitable for this invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenzene, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.

[0125] Suitable solvents based on aliphatic ketones for this invention include, but are not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, frankinc, phorone, isophorone, di-n-pentyl ketone, etc.; or aliphatic ethers, such as pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0126] Examples of ester-based solvents suitable for this invention include, but are not limited to: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Particularly preferred are methyl benzoate, octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate.

[0127] The solvent may be used alone or as a mixture of two or more organic solvents.

[0128] In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one pyrene organic compound, or a mixture thereof, as described above, and at least one organic solvent, and may further comprise another organic solvent. Examples of the other organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, naphthane, indene, and / or mixtures thereof.

[0129] In some preferred embodiments, solvents particularly suitable for the present invention are those with Hansen solubility parameters within the following ranges:

[0130] δd (dispersion force) is in the range of 17.0 to 23.2 MPa1 / 2, especially in the range of 18.5 to 21.0 MPa1 / 2;

[0131] δp (polar force) is in the range of 0.2 to 12.5 MPa1 / 2, especially in the range of 2.0 to 6.0 MPa1 / 2;

[0132] δh (hydrogen bond strength) is in the range of 0.9 to 14.2 MPa1 / 2, especially in the range of 2.0 to 6.0 MPa1 / 2.

[0133] In the compositions of the present invention, the boiling point of the organic solvent is taken into consideration when selecting it. In this invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; even more preferably ≥250°C; and most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead. The organic solvent can evaporate from the solvent system to form a thin film containing functional materials.

[0134] In a preferred embodiment, the composition according to the invention is a solution.

[0135] In another preferred embodiment, the composition according to the invention is a suspension.

[0136] The compositions in the embodiments of the present invention may include 0.01 wt% to 10 wt% of the compound or mixture according to the present invention, preferably 0.1 wt% to 5 wt%, more preferably 0.2 wt% to 5 wt%, and most preferably 0.25 wt% to 3 wt%.

[0137] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferably by a preparation method of printing or coating.

[0138] Suitable printing or coating technologies include (but are not limited to) inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot-loaded coating, etc. Gravure printing, inkjet printing, and other similar techniques are preferred. The solution or suspension may additionally include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, binders, etc., to adjust viscosity, film-forming properties, and improve adhesion.

[0139] This invention also provides the application of the pyrene-based organic compounds, mixtures, or compositions described above in organic electronic devices. The technical solution is as follows:

[0140] An organic electronic device includes a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode, said organic functional layers comprising pyrene-based organic compounds as described above, mixtures thereof, or prepared from the above-described compositions.

[0141] Further, the organic electronic device comprises a cathode, an anode, and at least one functional layer, wherein the functional layer comprises a pyrene-based organic compound, or a mixture thereof, or is prepared from the above-described composition. The functional layer is selected from hole injection layer (HIL), hole transport layer (HTL), light-emitting layer (EML), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), and hole blocking layer (HBL); preferably, the functional layer is selected from the light-emitting layer.

[0142] The organic electronic devices may be selected from, but are not limited to, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, etc., with organic electroluminescent devices, such as OLEDs and organic light-emitting field-effect transistors, being particularly preferred. OLEDs are especially preferred.

[0143] The light-emitting device described above, especially the OLED, includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0144] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting device. See, for example, Bulovic et al., Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or flexible. The substrate can be plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface. A substrate without surface defects is particularly desirable. In a preferred embodiment, the substrate is flexible and can be a polymer film or plastic with a glass transition temperature (Tg) of 150°C or higher, preferably 200°C or higher, more preferably 250°C or higher, and most preferably 300°C or higher. Examples of suitable flexible substrates include polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0145] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. Holes can be readily injected into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the light emitter in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known and can be readily selected by those skilled in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to fabricate devices according to the present invention.

[0146] The cathode may comprise a conductive metal or metal oxide. Electrons can be readily injected into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the luminescent material in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL), electron transport layer (ETL), or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials suitable for use as cathodes in OLEDs can be used as cathode materials for the devices of this invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0147] OLEDs may also include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated herein by reference.

[0148] In this embodiment of the invention, the pyrene-based organic compound is preferably used in the light-emitting layer of the OLED device.

[0149] In a preferred embodiment, the pyrene-based organic compound is preferably used as a blue light guest material, together with the blue light host material, in the emissive layer of the OLED device. Further, the blue light host material is selected from anthracene-based derivatives.

[0150] In a preferred embodiment, the light-emitting layer in the light-emitting device of the present invention is prepared using the composition of the present invention.

[0151] The light-emitting device according to the present invention has an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0152] The present invention also relates to the application of the organic electronic devices according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

[0153] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific Implementation

[0155] 1. Synthesis of compounds

[0156] Example 1: Synthesis of Compound 1

[0157]

[0158] Synthesis of intermediates 1-3:

[0159] Compounds 1-1 (10 mmol) and 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 1-3 was obtained with a molar weight of 9.17 mmol and a yield of 91.7%. MS (ASAP) = 338.

[0160] Synthesis of intermediates 1-5:

[0161] Intermediates 1-3 (10 mmol) and compounds 1-4 (20 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 1-5, with a molar weight of 7.84 mmol and a yield of 78.4%. MS (ASAP) = 211.

[0162] Synthesis of intermediates 1-7:

[0163] Intermediates 1-5 (10 mmol), compounds 1-6 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 1-7 was obtained with a molar weight of 7.05 mmol and a yield of 70.5%. MS (ASAP) = 287.

[0164] Synthesis of compound (1):

[0165] Intermediate 1-7 (20 mmol), compounds 1-8 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 1 was obtained in 76.8% yield. MS (ASAP) = 772.

[0166] Example 2

[0167]

[0168] Synthesis of intermediates 2-3:

[0169] Compound 2-1 (10 mmol) and compound 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 2-3 was obtained with a molar weight of 8.64 mmol and a yield of 86.4%. MS (ASAP) = 354.

[0170] Synthesis of intermediates 2-5:

[0171] Intermediate 2-3 (10 mmol) and compound 1-4 (20 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 2-5, with a molar weight of 7.35 mmol and a yield of 73.5%. MS (ASAP) = 227.

[0172] Synthesis of intermediates 2-7:

[0173] Intermediate 2-5 (10 mmol), compounds 1-6 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 2-7 was obtained with a molar weight of 5.63 mmol and a yield of 56.3%. MS (ASAP) = 303.

[0174] Synthesis of compound (2):

[0175] Intermediate 2-7 (20 mmol), compounds 1-8 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 2 was obtained in 45.9% yield. MS (ASAP) = 804.

[0176] Example 3

[0177]

[0178] Synthesis of intermediate 3-3:

[0179] Compound 3-1 (10 mmol) and compound 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 3-3 was obtained with a molar weight of 8.15 mmol and a yield of 81.5%. MS (ASAP) = 413.

[0180] Synthesis of intermediates 3-5:

[0181] Intermediate 3-3 (10 mmol) and compound 1-4 (20 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 3-5, with a molar weight of 7.18 mmol and a yield of 71.8%. MS (ASAP) = 286.

[0182] Synthesis of intermediates 3-7:

[0183] Intermediate 3-5 (10 mmol), compounds 1-6 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 3-7 was obtained with a molar weight of 5.45 mmol and a yield of 54.5%. MS (ASAP) = 362.

[0184] Synthesis of compound (3):

[0185] Intermediate 3-7 (20 mmol), compounds 1-8 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 3 was obtained in 43.2% yield. MS (ASAP) = 922.

[0186] Example 4

[0187]

[0188] Synthesis of compound (4):

[0189] Intermediate 1-7 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 4 was obtained in 52.3% yield. MS (ASAP) = 856.

[0190] Example 5

[0191]

[0192] Synthesis of compound (5):

[0193] Intermediate 2-7 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 5 was obtained in 67.3% yield. MS (ASAP) = 888.

[0194] Example 6

[0195]

[0196] Synthesis of compound (6):

[0197] Intermediate 3-7 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 6 was obtained in 32.7% yield. MS (ASAP) = 1006.

[0198] Example 7

[0199]

[0200] Synthesis of intermediate 7-2:

[0201] Intermediate 1-5 (10 mmol), compound 7-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 7-2 was obtained with a molar weight of 6.82 mmol and a yield of 68.2%. MS (ASAP) = 377.

[0202] Synthesis of compound (7):

[0203] Intermediate 7-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 7 was obtained in 55.6% yield. MS (ASAP) = 1036.

[0204] Example 8

[0205]

[0206] Synthesis of intermediate 8-2:

[0207] Intermediate 1-5 (10 mmol), compound 8-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 8-2 was obtained with a molar weight of 5.96 mmol and a yield of 59.6%. MS (ASAP) = 329.

[0208] Synthesis of compound (8):

[0209] Intermediate 8-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 8 was obtained in 70.3% yield. MS (ASAP) = 940.

[0210] Example 9

[0211]

[0212] Synthesis of intermediate 9-2:

[0213] Intermediate 1-5 (10 mmol), compound 9-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 9-2 was obtained with a molar weight of 8.16 mmol and a yield of 81.6%. MS (ASAP) = 377.

[0214] Synthesis of compound (9):

[0215] Intermediate 9-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 9 was obtained in 84.6% yield. MS (ASAP) = 1036.

[0216] Example 10

[0217]

[0218] Synthesis of intermediate 10-1:

[0219] Intermediate 2-5 (10 mmol), compound 7-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, the intermediate was obtained in a molar amount of 6.71 mmol, yield: 67.1%. MS (ASAP) = 393.

[0220] Synthesis of compound (10):

[0221] Intermediate 10-1 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 10 was obtained in 68.3% yield. MS (ASAP) = 1068.

[0222] Example 11

[0223]

[0224] Synthesis of intermediate 11-1:

[0225] Intermediate 2-5 (10 mmol), compound 8-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 11-1 was obtained with a molar weight of 7.84 mmol and a yield of 78.4%. MS (ASAP) = 345.

[0226] Synthesis of compound (11):

[0227] Intermediate 11-1 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 11 was obtained in 78.6% yield. MS (ASAP) = 972.

[0228] Example 12

[0229]

[0230] Synthesis of intermediates 2-5:

[0231] Intermediate 2-5 (10 mmol), compound 9-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 12-1 was obtained with a molar weight of 7.49 mmol and a yield of 74.9%. MS (ASAP) = 393.

[0232] Synthesis of compound (12):

[0233] Intermediate 12-1 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 12 was obtained in 79.3% yield. MS (ASAP) = 1068.

[0234] Example 13

[0235]

[0236] Synthesis of intermediate 13-2:

[0237] Intermediate 1-5 (10 mmol), compound 13-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 13-2 was obtained with a molar weight of 5.69 mmol and a yield of 56.9%. MS (ASAP) = 433.

[0238] Synthesis of compound (13):

[0239] Intermediate 13-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 13 was obtained in 68.7% yield. MS (ASAP) = 1148.

[0240] Example 14

[0241]

[0242] Synthesis of intermediate 14-1:

[0243] Intermediate 2-5 (10 mmol), compound 13-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 14-1 was obtained with a molar weight of 7.62 mmol and a yield of 76.2%. MS (ASAP) = 449.

[0244] Synthesis of compound (14):

[0245] Intermediate 14-1 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 14 was obtained in 70.5% yield. MS (ASAP) = 1180.

[0246] Example 15

[0247]

[0248] Synthesis of intermediate 15-2:

[0249] Intermediate 1-5 (10 mmol), compound 15-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 15-2 was obtained with a molar weight of 6.89 mmol and a yield of 68.9%. MS (ASAP) = 449.

[0250] Synthesis of compound (15):

[0251] Intermediate 15-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 15 was obtained in 70.4% yield. MS (ASAP) = 1180.

[0252] Example 16

[0253]

[0254] Synthesis of intermediate 16-3:

[0255] Intermediate 1-3 (10 mmol) and compound 16-2 (20 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 16-3, with a molar weight of 7.59 mmol and a yield of 75.9%. MS (ASAP) = 239.

[0256] Synthesis of intermediate 16-5:

[0257] Intermediate 16-3 (10 mmol), compound 16-4 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 16-5 was obtained with a molar weight of 8.34 mmol and a yield of 83.4%. MS (ASAP) = 365.

[0258] Synthesis of intermediate 16-6:

[0259] Intermediate 16-5 (10 mmol), compound 1-8 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 16-6 was obtained with a molar weight of 8.59 mmol and a yield of 85.9%. MS (ASAP) = 643.

[0260] Synthesis of intermediate 16-7:

[0261] Compounds 1-1 (10 mmol) and 1-2 (10 mmol) were dissolved in dichloromethane and stirred at room temperature for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, and the mixture was extracted, washed with water, and separated. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography to give intermediate 16-7 with a molar weight of 8.07 mmol and a yield of 80.7%. MS (ASAP) = 260.

[0262] Synthesis of intermediate 16-8:

[0263] Intermediate 16-7 (10 mmol) and compound 16-2 (10 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 16-8, with a molar weight of 7.23 mmol and a yield of 72.3%. MS (ASAP) = 211.

[0264] Synthesis of intermediate 16-9:

[0265] Intermediate 16-8 (10 mmol), compound 16-4 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 16-9 was obtained with a molar weight of 5.93 mmol and a yield of 59.3%. MS (ASAP) = 337.

[0266] Synthesis of compound (16):

[0267] Intermediate 16-9 (10 mmol), compound 16-6 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 16 was obtained in 42.8% yield. MS (ASAP) = 900.

[0268] Example 17

[0269]

[0270] Synthesis of intermediate 17-1:

[0271] Intermediate 1-5 (10 mmol), tert-butyl nitrite (30 mmol), and cuprous bromide (30 mmol) were dissolved in acetonitrile and stirred at 60 °C for 3 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 17-1 was obtained with a molar weight of 7.33 mmol and a yield of 73.3%. MS (ASAP) = 273.

[0272] Synthesis of intermediate 17-3:

[0273] Intermediate 17-1 (10 mmol) and compound 17-2 (10 mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction, washing with water, and separation. The organic phase was collected, dried, concentrated under reduced pressure, and subjected to column chromatography and recrystallization to give intermediate 17-3, with a molar weight of 8.22 mmol and a yield of 82.2%. MS (ASAP) = 287.

[0274] Synthesis of intermediate 17-4:

[0275] Intermediate 17-3 (10 mmol), compound 9-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 17-4 was obtained with a molar weight of 8.39 mmol and a yield of 83.9%. MS (ASAP) = 453.

[0276] Synthesis of compound (17):

[0277] Intermediate 17-4 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 17 was obtained in 76.3% yield. MS (ASAP) = 1188.

[0278] Example 18

[0279]

[0280] Synthesis of intermediate 18-2:

[0281] Intermediate 1-5 (10 mmol), compound 18-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 18-2 was obtained with a molar weight of 5.33 mmol and a yield of 53.3%. MS (ASAP) = 315.

[0282] Synthesis of compound (18):

[0283] Intermediate 18-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 18 was obtained in 64.2% yield. MS (ASAP) = 912.

[0284] Example 19

[0285]

[0286] Synthesis of intermediate 19-2:

[0287] Intermediate 1-5 (10 mmol), compound 19-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was extracted, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, intermediate 19-2 was obtained with a molar weight of 7.59 mmol and a yield of 75.9%. MS (ASAP) = 363.

[0288] Synthesis of compound (19):

[0289] Intermediate 19-2 (20 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 °C for 6 h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the extract was obtained, washed with water, and the organic phase was collected. After drying, concentration under reduced pressure, and column chromatography, compound 19 was obtained in 78.7% yield. MS (ASAP) = 1008.

[0290] 2. Testing

[0291] The structure of some of the functional materials involved in the testing section is as follows:

[0292]

[0293] (1) Compound energy levels

[0294] The energy levels of organic compound materials can be obtained through quantum computing, such as using TD-DFT (time-dependent density functional theory) via Gaussian09W (Gaussian Inc.). Specific simulation methods can be found in WO2011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). Then, the energy structure of the organic molecule is calculated using TD-DFT (time-dependent density functional theory) to obtain "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). HOMO and LUMO energy levels are calculated according to the following calibration formulas, with S1, T1, and the resonance factor f(S1) used directly.

[0295] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0296] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0297] HOMO, LUMO, T1, and S1 are direct calculation results from Gaussian 09W, in Hartree units. The results are shown in Table 1 below:

[0298] Table 1

[0299]

[0300]

[0301] (2) Fabrication and characterization of OLED devices

[0302] The fabrication process of the OLED device using the above-mentioned compound is described in detail below through specific device embodiments. The structure of the OLED device is: substrate / ITO anode / HIL / HTL / EML / ETL / cathode. Please refer to the appendix. Figure 1 101 is the substrate, 102 is the ITO anode, 103 is the hole injection layer (HIL), 104 is the hole transport layer (HTL), 105 is the light-emitting layer, 106 is the electron transport layer (ETL), and 107 is the cathode.

[0303] The preparation steps of OLDE-1 are as follows:

[0304] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrate: Clean with chloroform, then perform ultraviolet ozone treatment;

[0305] b. HIL (hole injection layer, 40nm): 60nm PEDOT (polyethylene dioxythiophene, Clevios) was prepared on ITO by spin coating in a cleanroom environment. TM AI4083) was used as HIL and treated on a hot plate at 180°C for 10 minutes;

[0306] c. HTL (hole transport layer, 20nm): 20nm PVK (Sigma Aldrich, average Mn 25,000-50,000) was prepared by spin coating onto HIL in a nitrogen glove box with a toluene solution of PVK. The solution concentration was 5mg / ml. Then it was treated on a hot plate at 180°C for 60 minutes.

[0307] d. EML (Organic Light Emitting Layer, 40nm): In a nitrogen glove box, a methyl benzoate solution (host-guest weight ratio of 95:5) was applied to HTL by spin coating with a solution concentration of 15mg / ml. The solution was then treated on a hot plate at 140°C for 10 minutes. The host structure was BH, and the guest was compound 1 prepared in Example 1 above.

[0308] e. Electron transport layer and cathode: The heat-treated substrate is transferred to a vacuum chamber, and then ET and Liq are placed in different evaporation units and co-deposited in a high vacuum (1×10-6 mbar) at a ratio of 50% by weight to form a 20 nm electron transport layer on the light-emitting layer, followed by the deposition of an Al cathode with a thickness of 100 nm.

[0309] f. Encapsulation: The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0310] The preparation steps of OLDE-2 to OLDE-Ref are basically the same as those of OLDE-1, except that the guest material is replaced by the guest material shown in Table 2 instead of compound 1.

[0311] The current-voltage (JV) characteristics of each OLED device were characterized using a characterization device, and important parameters such as efficiency, lifetime and external quantum efficiency were recorded. The results are shown in Table 2.

[0312] Table 2

[0313]

[0314]

[0315] As shown in Table 2, on the one hand, the blue light-emitting devices prepared using compounds 1-19 as guest materials in the EML layer exhibit superior color coordinates compared to the comparative compound 1, demonstrating better deep blue emission. On the other hand, the luminous efficiency of the blue light-emitting devices prepared using compounds 1-19 as guest materials in the EML layer is in the range of 8-9 cd / A, showing superior luminous efficiency. This is because, compared to the comparative compound 1, the present invention introduces an alkyl group at the ortho position of dibenzofuran (comparative compound 1 is dibenzofuran), which increases molecular solubility, improves molecular purification ability, and thus improves molecular purity, thereby improving device performance. Furthermore, introducing ortho-dibenzofuran derivatives or dibenzothiophene derivatives (OLED-7,10,13,14,15) on the other side of the amino group improves molecular conjugation, thereby improving device performance. In addition, the lifetime of the blue light-emitting devices prepared using compounds 1-19 as guest materials in the EML layer is also superior to that of the comparative compound 1.

[0316] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0317] The above-described embodiments are merely illustrative of several implementation methods of the present invention, facilitating a detailed understanding of the technical solutions of the present invention, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided by the present invention through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this invention patent should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A pyrene-based organic compound, characterized in that, It has the structure shown in general formula (V-1): in: Each occurrence of Ar2-Ar3 is independently selected from the following groups: ， in: R 101 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms; m2 is selected from 0, 1, 2, 3 or 4; m3 is selected from 0, 1, 2 or 3; R 10 R 11 Each occurrence is independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms; Each of R1-R8 is independently selected from -H, -D, or straight-chain alkyl with 1 to 10 C atoms, or branched alkyl with 3 to 10 C atoms, or cyclic alkyl with 3 to 10 C atoms. * indicates a connection point.

2. The pyrene-based organic compound according to claim 1, characterized in that, Each occurrence of Ar2-Ar3 has the following structure or .

3. A pyrene-based organic compound, characterized in that, It has any of the following structures: 。 4. A mixture, characterized in that, It comprises a pyrene-based organic compound and an organic functional material as described in any one of claims 1 to 3, wherein the organic functional material is selected from at least one of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials, and organic dyes.

5. A composition, characterized in that, It comprises at least one pyrene-based organic compound as described in any one of claims 1 to 3, or the mixture as described in claim 4, and at least one organic solvent.

6. An organic electronic device comprising a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode, characterized in that, The organic functional layer is selected from the light-emitting layer, which contains a pyrene-based organic compound as described in any one of claims 1 to 3, or a mixture as described in claim 4, or is prepared from the composition as described in claim 5.

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