Silicon-containing organic compounds, mixtures, compositions and organic electronic devices

Abstract

The present application provides a kind of silicon-containing organic compound, mixture, composition and organic electronic device.The structure of the silicon-containing organic compound is shown in general formula (1), the silicon-containing organic compound can be used as a light-emitting material in the functional layer of electronic device, improve the efficiency and life of device.

Description

Technical Field

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

[0002] Organic light-emitting diodes (OLEDs) have the advantages of low cost, light weight, low operating voltage, high brightness, color tunability, wide viewing angle, easy assembly, and low energy consumption in flat panel displays and lighting applications, making them the most promising display technology.

[0003] The principle behind light emission in organic electronic devices is organic electroluminescence, which refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic electroluminescent devices typically have a positive electrode, a negative electrode, and a functional layer containing organic material between them. To improve the efficiency and lifetime of organic electroluminescent elements, the functional layer has a multi-layered structure, with each layer containing different organic materials. Specifically, these include hole injection layers, hole transport layers, light-emitting layers, electron transport layers, or electron injection layers. In organic electroluminescent 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 organic electroluminescent elements 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 luminescent material systems based on fluorescence and phosphorescence have been developed. Among these, OLEDs using fluorescent materials exhibit high reliability, but their internal electroluminescence quantum efficiency under electrical excitation is limited to 25% due to the 1:3 branching ratio of singlet to triplet excited states of the exciton. OLEDs using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency, but phosphorescent OLEDs face a major challenge: the roll-off effect, where luminous efficiency rapidly decreases with increasing current or brightness, which is particularly detrimental to high-brightness applications.

[0005] To date, the only phosphorescent materials with practical application value are iridium and platinum complexes. These raw materials are rare and expensive, and the synthesis of these complexes is complex, resulting in high costs. To overcome these problems, Adachi proposed the concept of reverse internal conversion, which allows the use of organic compounds, i.e., without the use of metal complexes, to achieve high efficiency comparable to phosphorescent OLEDs. This concept has been realized through various material combinations, such as: 1) utilizing composite excited states; 2) utilizing thermally excited delayed fluorescence (TADF) materials.

[0006] Traditional red and green TADF materials have achieved good results in various performance aspects, but compared with phosphorescent materials, their performance still lags behind in terms of both efficiency and lifespan. Summary of the Invention

[0007] Based on this, the present invention provides a silicon-containing organic compound that can be used as a luminescent material in the functional layer of electronic devices to extend the luminescent efficiency and lifespan of the devices.

[0008] The present invention is achieved through the following technical solution.

[0009] A silicon-containing organic compound, the structure of which is shown in general formula (1):

[0010]

[0011] in:

[0012] X1, X2, and X3 are each independently selected from CR5 or N, and at least one of X1, X2, and X3 is selected from N;

[0013] Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, and alkyl groups having 3 to 30 carbon atoms, respectively.

[0014] R1, R2, R3, R4, and R5, each appearing independently, are 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 alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, branched alkoxy groups having 3 to 20 carbon atoms, cyclic alkoxy groups having 3 to 20 carbon atoms, branched thioalkoxy groups having 3 to 20 carbon atoms, cyclic thioalkoxy groups having 3 to 20 carbon atoms, silyl groups, ketone groups having 1 to 20 carbon atoms, and others. Alkoxycarbonyl with 2 to 20 carbon atoms, aryloxycarbonyl with 7 to 20 carbon atoms, alkenyl, carbamoyl, halocarbamoyl, formyl, cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF3, -Cl, -Br, -F, substituted or unsubstituted aromatic group with 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 30 ring atoms, substituted or unsubstituted aryloxy group with 6 to 30 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 30 ring atoms, or combinations of these groups;

[0015] n is selected from 1, 2, 3, 4, or 5;

[0016] m can be selected from 1, 2, 3 or 4.

[0017] The present invention also provides a mixture comprising the silicon-containing organic compound as described above, and at least one organic functional material selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitters, host materials, or organic dyes.

[0018] The present invention also provides a composition comprising a silicon-containing organic compound as described above or a mixture thereof, and at least one organic solvent.

[0019] The present invention also provides an organic electronic device comprising a functional layer made of a silicon-containing organic compound as described above, a mixture as described above, or a composition as described above.

[0020] Compared with the prior art, the silicon-containing organic compounds of the present invention have the following beneficial effects:

[0021] When the DA system described in this invention is used as a light-emitting object in organic electroluminescent devices, it is beneficial to improve the exciton utilization and device stability of OLED devices, thereby achieving the goal of improving device luminous efficiency and lifetime. Detailed Implementation

[0022] To facilitate understanding of the present invention, a more complete description will be given below with reference to relevant embodiments. Preferred embodiments of the invention are shown in the embodiments. However, 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.

[0023] 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 description of the 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.

[0024] In this invention, the terms "composition" and "printing ink" or "ink" have the same meaning and can be used interchangeably.

[0025] In this invention, aromatic groups, aromatic families, and aromatic ring systems have the same meaning and can be used interchangeably.

[0026] In this invention, heteroaromatic groups, heteroaromatic families, and heteroaromatic ring systems have the same meaning and can be used interchangeably.

[0027] In this invention, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0028] 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 not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-20 C 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, haloformyl, formyl, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, and the above groups may also be further substituted by substituents acceptable in the art; it is understood that R' and R" in -NR'R" are each independently selected from, but not limited to: H, deuterium The group R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms. Preferably, R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-10 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, and the above groups may be further substituted with substituents acceptable in the art.

[0029] In this invention, "ring atom number" refers to the number of atoms in the ring itself 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.

[0030] "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, "substituted or unsubstituted aryl having 6 to 40 ring atoms" means an aryl containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl having 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, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl 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.

[0031] "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, "substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted heteroaryl group having 6 to 14 ring atoms, and the heteroaryl group may optionally be further substituted. Suitable examples include, but are not limited to: thiophene, furanyl, pyrrole, imidazolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, etc. Pyridyl, triazinyl, acridineyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiopheneyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrololyl, thienopyrrololyl, thienopyrrololyl, furanolololyl, furanolofuranyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridine, primidyl, quinazolinone, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0032] In this invention, "alkyl" can refer to straight-chain, branched, and / or cyclic alkyl groups. The number of carbon atoms in an alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 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, adamantyl, etc.

[0033] "Halogen" or "halogen group" refers to F, Cl, Br or I.

[0034] 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).

[0035] In this invention, "*" represents a connection site.

[0036] 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.

[0037] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring; such as express Can be with A fused ring can be formed at any position on the benzene ring.

[0038] This invention provides a silicon-containing organic compound with the structure shown in general formula (1):

[0039]

[0040] in:

[0041] X1, X2, and X3 are each independently selected from CR5 or N, and at least one of X1, X2, and X3 is selected from N;

[0042] Ar1 and Ar2 are each independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, or alkyl groups having 1 to 30 carbon atoms;

[0043] R1, R2, R3, R4, and R5, each appearing independently, are 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 alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, branched alkoxy groups having 3 to 20 carbon atoms, cyclic alkoxy groups having 3 to 20 carbon atoms, branched thioalkoxy groups having 3 to 20 carbon atoms, cyclic thioalkoxy groups having 3 to 20 carbon atoms, silyl groups, ketone groups having 1 to 20 carbon atoms, and others. Alkoxycarbonyl with 2 to 20 carbon atoms, aryloxycarbonyl with 7 to 20 carbon atoms, alkenyl, carbamoyl, halocarbamoyl, formyl, cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF3, -Cl, -Br, -F, substituted or unsubstituted aromatic group with 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 30 ring atoms, substituted or unsubstituted aryloxy group with 6 to 30 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 30 ring atoms, or combinations of these groups;

[0044] n is selected from 1, 2, 3, 4, or 5;

[0045] m can be selected from 1, 2, 3 or 4.

[0046] Understandably, in this invention, m and n represent the number of R4 and R3 connected to the benzene ring, respectively.

[0047] In a specific example, the structures of silicon-containing organic compounds are shown in general formulas (2-1) to (2-4):

[0048]

[0049] In one example, Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 25 ring atoms, and substituted or unsubstituted heteroaromatic groups having 6 to 25 ring atoms, respectively.

[0050] In a specific example, Ar1 and Ar2 are each independently selected from the following groups:

[0051]

[0052] in:

[0053] Each time X4 appears, it is independently selected from CR6 or N;

[0054] Y1 is independently selected from CR7R8, NR9, SiR7R8, O, S, Se, S=O, S(=O)2, or PR9;

[0055] R6, R7, R8, and R9, each appearing independently, are 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, and groups having 1 to 20 carbon atoms. Ketoyl groups, alkoxycarbonyl groups having 2 to 20 carbon atoms, aryloxycarbonyl groups having 7 to 20 carbon atoms, cyano, carbamoyl, halocarbamoyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 20 ring atoms, aryloxy or heteroaromatic groups having 5 to 20 ring atoms, or combinations of these groups.

[0056] Understandably, when X4 is a connection site, X4 is selected from C.

[0057] More specifically, each time Ar1 and Ar2 appear, they are independently selected from the following groups:

[0058]

[0059] Where: * indicates a connection site.

[0060] In a specific example, R6, R7, R8, and R9 each appear independently selected from: -H, -D, straight-chain alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, cyano, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 10 cyclic atoms.

[0061] More specifically, each time Ar1 and Ar2 appear, they are independently selected from the following groups:

[0062]

[0063] * indicates a connection point.

[0064] Preferably, Ar1 and Ar2 are each independently selected from the following groups each time they appear:

[0065]

[0066] More preferably, Ar1 is selected from Ar2 is selected from

[0067] Preferably, each of R6, R7, R8, and R9 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 8 carbon atoms, a branched or cyclic alkyl group having 3 to 8 carbon atoms, cyano, nitro, -CF3, -Cl, -Br, -F, -I, phenyl, biphenyl, pyridyl, pyrimidinyl, triazine, naphthyl, quinolinyl, isoquinolinyl, or a combination of these groups.

[0068] Preferably, X1, X2 and X3 are selected from N.

[0069] In a specific example, R1, R2, R3, R4, and R5 each appear 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, a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, -CF3, -Cl, -Br, -F, a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.

[0070] More specifically, each time R1 and R2 appear, they are independently selected from: -H, -D, straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, silyl groups, cyano, isocyano, hydroxyl, nitro, -CF3, -Cl, -Br, -F, substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms, or combinations of these groups.

[0071] More specifically, each occurrence of R1 and R2 is 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-methyl Hexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, triazine, pyridyl, pyrimidinyl, imidazolyl, furanyl, thiophene, benzofuranyl, benzothiophene, indolyl, carbazolyl, dibenzothiophene, dibenzofuranyl, phenyl-substituted carbazolyl, fluorenyl, alkyl-substituted fluorenyl having 1-10 carbon atoms.

[0072] Preferably, R1 and R2 are selected from the same group.

[0073] In one embodiment, each occurrence of R3 is independently selected from: -H, -D, straight-chain alkyl having 1 to 8 carbon atoms, branched alkyl having 3 to 8 carbon atoms, cyclic alkyl having 3 to 8 carbon atoms, silyl, cyano, isocyano, hydroxyl, nitro, -CF3, -Cl, -Br, -F, or phenyl, or biphenyl, or pyridyl, or pyrimidinyl, or triazine.

[0074] In a specific example, the silicon-containing compound is a thermally excited delayed fluorescence material.

[0075] Specifically, the silicon-containing organic compounds according to the present invention are selected from, but not limited to, the following structures:

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094] The silicon-containing 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, hosts, and organic dyes.

[0095] In one specific example, the silicon-containing organic compound according to the invention is used in the light-emitting layer, preferably as a guest material in the light-emitting layer. Preferably, the silicon-containing organic compound according to the invention is used in a green organic light-emitting device.

[0096] This invention further relates to a mixture comprising at least one silicon-containing 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.

[0097] The present invention also relates to a composition comprising at least one silicon-containing 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.

[0098] In a preferred example, a composition according to the invention is characterized in that the at least one organic solvent is selected from aromatic or heteroaromatic solvents.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] The solvent may be used alone or as a mixture of two or more organic solvents.

[0105] In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one silicon-containing 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.

[0106] In some preferred examples, solvents particularly suitable for the present invention are those with Hansen solubility parameters within the following ranges:

[0107] 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;

[0108] 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;

[0109] 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.

[0110] 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.

[0111] In a preferred embodiment, the composition according to the invention is a solution.

[0112] In another preferred embodiment, the composition according to the invention is a suspension.

[0113] The compositions in the embodiments of the present invention may include 0.01 wt% to 10 wt% of a silicon-containing organic 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%.

[0114] 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.

[0115] 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.

[0116] This invention also provides the application of the silicon-containing organic compounds, mixtures, or compositions described above in organic electronic devices. The technical solution is as follows:

[0117] An organic electronic device comprising a silicon-containing organic compound, mixture, or functional layer prepared from the above-described composition as described above.

[0118] 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 at least one organic functional layer comprises a silicon-containing organic compound, a mixture thereof, or a composition thereof as described above.

[0119] Further, the organic electronic device comprises a cathode, an anode, and at least one organic functional layer, wherein the at least one organic functional layer comprises a silicon-containing organic compound, or a mixture thereof, as described above, or is prepared from the above-described composition. The organic 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 organic functional layer is selected from the light-emitting layer.

[0120] 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.

[0121] The light-emitting device described above, especially the OLED, includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0122] 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).

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] The present invention also relates to the application of the organic electronic devices according to the present invention in various electronic devices, including but not limited to: display devices, lighting devices, light sources, sensors, etc.

[0128] The present invention also relates to electronic devices comprising organic electronic devices according to the present invention, including but not limited to: display devices, lighting devices, light sources, sensors, etc.

[0129] 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

[0131] The silicon-containing organic compounds and their preparation methods of the present invention will be further described in detail below with reference to specific embodiments. Unless otherwise specified, all raw materials used in the following embodiments are commercially available products.

[0132] 1.1 Synthesis of Compounds

[0133] Example 1

[0134] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0135]

[0136] Synthesis of Intermediate 1-1: Phenyrazine (10 g, 54.6 mmol), bromobenzene (17 g, 109 mmol), Pd2(dba)3 (1.48 g, 1.6 mmol), t-Bu3P (0.39 g, 1.94 mmol), and sodium tert-butoxide (15.5 g, 162 mmol) were weighed into a 500 mL three-necked flask. 200 mL of toluene was added, and the atmosphere was replaced with nitrogen. The reaction was carried out at 80 °C for 12 h. The product was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE) to give a white solid in 80% yield. MS (ASAP) = 259.1.

[0137] Synthesis of intermediate 1-2: Intermediate 1-1 (11 g, 42.5 mmol) was placed in a 500 mL two-necked flask, and 200 mL of DMF was added until the solid was completely dissolved. NBS (7.5 g, 42.5 mmol) was weighed and placed in a constant pressure dropping funnel, dissolved in 100 mL of DMF, and added slowly. The reaction was carried out at room temperature for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE) to give a white solid in 85% yield. MS (ASAP) = 337.0.

[0138] Synthesis of intermediates 1-3: Prepare a dry 500mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen. Maintain nitrogen flow in the reaction flask, weigh 1,4-dibromobenzene (10g, 42.6mmol), and add THF (250mL). Evacuate and purge with nitrogen three times, then cool to -78℃. Slowly add n-butyllithium solution (17.4mL, 42.6mmol) dropwise to the reaction flask. After reacting at -78℃ for 30min, quickly add dimethoxydiphenylsilane (10.4g, 42.6mmol). Allow the reaction system to slowly rise to room temperature and react for 12h. Add water, extract with DCM, evaporate the solvent, and then perform column chromatography (eluent: PE) to obtain a colorless oily substance in 41% yield. MS (ASAP) = 368.0.

[0139] Synthesis of intermediates 1-4: Prepare a dry 250 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen; maintain nitrogen flow in the reaction flask, weigh 1-2 (3.0 g, 8.9 mmol), and add THF (100 mL), evacuate and purge with nitrogen three times, then cool to -78 °C; slowly add n-butyllithium solution (3.6 mL, 8.9 mmol) dropwise to the reaction flask, react at -78 °C for 60 min, then quickly add 1-3 (3.3 g, 8.9 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and slurry with PE to obtain a white solid. Yield 67%. MS (ASAP) = 595.1.

[0140] Synthesis of intermediates 1-5: 1-4 (6 g, 10 mmol), (Bpin)2 (3.8 g, 15 mmol), AcOK (9.8 g, 100 mmol), Pd(dppf)Cl2 (0.74 g, 1.0 mmol), and t-Bu3P (0.39 g, 1.94 mmol) were weighed into a 250 mL three-necked flask. 100 mL of 1,4-dioxane was added, and the atmosphere was replaced with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 5:1) to give a colorless oily substance in 93% yield. MS (ASAP) = 643.3.

[0141] Synthesis of Compound 1: 1-5 (6 g, 9.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.8 g, 14 mmol), K₂CO₃ (12.8 g, 93 mmol), and Pd(PPh₃)₄ (1.1 g, 0.93 mmol) were weighed into a 250 mL three-necked flask. 100 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 50% yield. MS (ASAP) = 748.3.

[0142] Example 2

[0143] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0144]

[0145] Synthesis of Intermediate 2-1: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen. Maintain nitrogen flow in the reaction flask, weigh 1,3-dibromobenzene (10 g, 42.6 mmol), and add THF (250 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (17.4 mL, 42.6 mmol) to the reaction flask. After reacting at -78 °C for 30 min, quickly add dimethoxydiphenylsilane (10.4 g, 42.6 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and then perform column chromatography (eluent: PE) to obtain a colorless oil in 35% yield. MS (ASAP) = 368.0.

[0146] Synthesis of intermediate 2-2: Prepare a dry 250 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen; maintain nitrogen flow in the reaction flask, weigh 1-2 (3.0 g, 8.9 mmol), and add THF (100 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (3.6 mL, 8.9 mmol) to the reaction flask, react at -78 °C for 60 min, then quickly add 2-1 (3.3 g, 8.9 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and slurry with PE to obtain a white solid. Yield: 55%. MS (ASAP) = 595.1.

[0147] Synthesis of intermediate 2-3: 2-2 (6 g, 10 mmol), (Bpin)2 (3.8 g, 15 mmol), AcOK (9.8 g, 100 mmol), Pd(dppf)Cl2 (0.74 g, 1.0 mmol), and t-Bu3P (0.39 g, 1.94 mmol) were weighed into a 250 mL three-necked flask. 100 mL of 1,4-dioxane was added, and nitrogen was purged. The reaction was carried out at 100 °C for 12 h. The product was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 5:1) to give a colorless oily substance in 70% yield. MS (ASAP) = 643.3.

[0148] Synthesis of Compound 2: 2-3 (6 g, 9.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.8 g, 14 mmol), K₂CO₃ (12.8 g, 93 mmol), and Pd(PPh₃)₄ (1.1 g, 0.93 mmol) were weighed into a 250 mL three-necked flask. 100 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 50% yield. MS (ASAP) = 748.3.

[0149] Example 3

[0150] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0151]

[0152] Synthesis of intermediate 3-1: 10 g (38.3 mmol) of 2-bromophenoxazine, 15.6 g (76.6 mmol) of iodobenzene, 1.48 g (1.6 mmol) of Pd2(dba)3, 0.39 g (1.94 mmol) of t-Bu3P, and 15.5 g (162 mmol) of sodium tert-butoxide were weighed into a 500 mL three-necked flask. 200 mL of toluene was added, and nitrogen was used to replace the atmosphere. The mixture was reacted at 80 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE) to give a white solid in 65% yield. MS (ASAP) = 337.0.

[0153] Synthesis of intermediate 3-2: Prepare a dry 250 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen; maintain nitrogen flow in the reaction flask, weigh 3-1 (3.0 g, 8.9 mmol), and add THF (100 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (3.6 mL, 8.9 mmol) to the reaction flask, react at -78 °C for 60 min, then quickly add 1-3 (3.3 g, 8.9 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and slurry with PE to obtain a white solid. Yield: 49%. MS (ASAP) = 595.1.

[0154] Synthesis of intermediate 3-3: 3-2 (6 g, 10 mmol), (Bpin)2 (3.8 g, 15 mmol), AcOK (9.8 g, 100 mmol), Pd(dppf)Cl2 (0.74 g, 1.0 mmol), and t-Bu3P (0.39 g, 1.94 mmol) were weighed into a 250 mL three-necked flask. 100 mL of 1,4-dioxane was added, and the atmosphere was replaced with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 5:1) to give a colorless oily substance in 77% yield. MS (ASAP) = 643.3.

[0155] Synthesis of Compound 3: 3-3 (6 g, 9.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.8 g, 14 mmol), K₂CO₃ (12.8 g, 93 mmol), and Pd(PPh₃)₄ (1.1 g, 0.93 mmol) were weighed into a 250 mL three-necked flask. 100 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 43% yield. MS (ASAP) = 748.3.

[0156] Example 4

[0157] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0158]

[0159] Synthesis of compound 4: 1-5 (10 g, 15.5 mmol), 4-chloro-2,6-diphenylpyrimidine (8.3 g, 31.1 mmol), K₂CO₃ (21.3 g, 155 mmol), and Pd(PPh₃)₄ (1.8 g, 1.6 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 56% yield. MS (ASAP) = 747.3.

[0160] Example 5

[0161] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0162]

[0163] Synthesis of Compound 5: 1-5 (8 g, 12.4 mmol), 4-chloro-2,6-diphenylpyridine (6.6 g, 24.8 mmol), K₂CO₃ (17.1 g, 124 mmol), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 53% yield. MS (ASAP) = 746.3.

[0164] Example 6

[0165] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0166]

[0167] Synthesis of Compound 6: 1-5 (8 g, 12.4 mmol), 4-chloro-2-phenyl-6-naphthyl-1,3,5-triazine (7.9 g, 24.8 mmol), K₂CO₃ (17.1 g, 124 mmol), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 47% yield. MS (ASAP) = 796.3.

[0168] Example 7

[0169] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0170]

[0171] Synthesis of Compound 7: 1-5 (8 g, 12.4 mmol), 4-chloro-2-phenyl-6-biphenyl-1,3,5-triazine (8.5 g, 24.8 mmol), K₂CO₃ (17.1 g, 124 mmol), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 42% yield. MS (ASAP) = 824.3.

[0172] Example 8

[0173] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0174]

[0175] Synthesis of compound 8-1: Dibenzofuran-3-boronic acid (10 g, 47 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (10.6 g, 47 mmol), K₂CO₃ (32.5 g, 236 mmol), and Pd(PPh₃)₄ (5.5 g, 4.7 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE, yield: 80%) to give a white solid. MS (ASAP) = 357.1.

[0176] Synthesis of compound 8: 1-5 (8 g, 12.4 mmol), 8-1 (8.8 g, 24.8 mmol), K₂CO₃ (17.1 g, 124 mmol), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 49% yield. MS (ASAP) = 838.3.

[0177] Example 9

[0178] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0179]

[0180] Synthesis of compound 9-1: 3-Borate-9,9-dimethylfluorene (5 g, 21 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (4.7 g, 21 mmol), K₂CO₃ (14.5 g, 105 mmol), and Pd(PPh₃)₄ (2.4 g, 2.1 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE, yield: 84%) to give a white solid. MS (ASAP) = 383.1.

[0181] Synthesis of compound 9: 3-3 (5 g, 7.8 mmol), 9-1 (6.0 g, 15.6 mmol), K2CO3 (5.4 g, 38.9 mmol), and Pd(PPh3)4 (0.90 g, 0.78 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 42% yield. MS (ASAP) = 864.3.

[0182] Example 10

[0183] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0184]

[0185] Synthesis of compound 10-1: N-phenyl-3-carbazoleboric acid (5.0 g, 17.4 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (3.9 g, 17.4 mmol), K₂CO₃ (12 g, 87 mmol), and Pd(PPh₃)₄ (2.0 g, 1.7 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE, yield: 89%) to give a white solid. MS (ASAP) = 432.1.

[0186] Synthesis of Compound 10: 3⁻³ (5 g, 7.8 mmol), 10⁻¹ (6.7 g, 15.6 mmol), K₂CO₃ (5.4 g, 38.9 mmol), and Pd(PPh₃)₄ (0.90 g, 0.78 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 55% yield. MS (ASAP) = 913.3.

[0187] Example 11

[0188] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0189]

[0190] Synthesis of Compound 11: 1-5 (8 g, 12.4 mmol), 4-chloro-2,6-(3-pyridyl)-1,3,5-triazine (7.9 g, 24.8 mmol), K₂CO₃ (17.1 g, 124 mmol), and Pd(PPh₃)₄ (1.4 g, 1.2 mmol) were weighed into a 250 mL three-necked flask. 150 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 47% yield. MS (ASAP) = 750.3.

[0191] Example 12

[0192] This embodiment provides a silicon-containing organic compound, and the specific synthetic route is as follows:

[0193]

[0194] Synthesis of Intermediate 12-1: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen. Maintain nitrogen flow in the reaction flask, weigh 1,4-dibromobenzene (10 g, 42.6 mmol), and add THF (250 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (17.4 mL, 42.6 mmol) dropwise to the reaction flask. After reacting at -78 °C for 30 min, rapidly add dimethoxybis(4-tert-butylphenyl)silane (15 g, 42.6 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and then perform column chromatography (eluent: PE) to obtain a colorless oil in 33% yield. MS (ASAP) = 480.2.

[0195] Synthesis of intermediate 12-2: Prepare a dry 250 mL three-necked flask, set up the reaction apparatus, evacuate, and purge with nitrogen; maintain nitrogen flow in the reaction flask, weigh 1-2 (3.0 g, 8.9 mmol), and add THF (100 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (3.6 mL, 8.9 mmol) to the reaction flask, react at -78 °C for 60 min, then quickly add 12-1 (4.3 g, 8.9 mmol). Allow the reaction system to slowly rise to room temperature and react for 12 h. Add water, extract with DCM, evaporate the solvent, and slurry with PE to obtain a white solid. Yield: 52%. MS (ASAP) = 707.2.

[0196] Synthesis of intermediate 12-3: 12-2 (5 g, 7.1 mmol), (Bpin)2 (2.2 g, 8.5 mmol), AcOK (7.0 g, 71 mmol), Pd(dppf)Cl2 (0.74 g, 1.0 mmol), and t-Bu3P (0.39 g, 1.94 mmol) were weighed into a 250 mL three-necked flask. 100 mL of 1,4-dioxane was added, and nitrogen was purged. The reaction was carried out at 100 °C for 12 h. The product was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 5:1) to give a colorless oily substance in 82% yield. MS (ASAP) = 755.4.

[0197] Synthesis of Compound 12: 12-3 (5 g, 6.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.5 g, 13 mmol), K₂CO₃ (9.1 g, 66 mmol), and Pd(PPh₃)₄ (0.77 g, 0.66 mmol) were weighed into a 250 mL three-necked flask. 100 mL of toluene, 50 mL of ethanol, and 50 mL of water were added, and the atmosphere was purged with nitrogen. The reaction was carried out at 100 °C for 12 h. The solution was evaporated to dryness, washed with water, and subjected to column chromatography (eluent: PE:DCM = 3:1) to give a white solid in 51% yield. MS (ASAP) = 860.4.

[0198] 1.2 Fabrication of OLED Devices

[0199] In this embodiment, in the green light device, the main material is selected from GH, HATCN is used as the hole injection layer material, HT is used as the hole transport material, GP is used as the electron blocking layer material, compounds 1-12 of this application are used as dopants (GD) for the light-emitting material, ET is used as the electron transport material, and Liq (lithium 8-hydroxyquinoline) is used as the electron injection material. The device structure is ITO / HATCN / HT / GP / GH:GD(8%wt) / ET:Liq / Liq / Al.

[0200] The compound structures involved in the fabrication of OLED devices are as follows:

[0201]

[0202] The above-mentioned materials HATCN, HT, GP, GH, GD(ref), ET, and Liq are all commercially available, or their synthesis methods are existing technologies.

[0203] The following specific examples illustrate the fabrication process of OLED devices using the above-mentioned materials.

[0204] Device Example 1

[0205] The method for fabricating an OLED device in this embodiment includes the following steps:

[0206] 1) Cleaning of ITO (Indium Tin Oxide) Anode Layer: Clean the ITO conductive glass anode layer, then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes, and then treat it in a plasma cleaner for 5 minutes to improve the electrode power function.

[0207] 2) Formation of the hole injection layer: On the ITO anode layer, the hole injection layer material HATCN is deposited by vacuum evaporation, with a thickness of 30 nm, and the evaporation rate is...

[0208] 3) Formation of hole transport layer: Hole transport material HT is deposited on the hole injection layer by vacuum evaporation, with a thickness of 60nm;

[0209] 4) Forming an electron blocking layer: Electron blocking layer material GP is deposited on top of the hole transport layer, with a thickness of 10 nm;

[0210] 5) Formation of the light-emitting layer: The light-emitting layer is deposited on the electron blocking layer. GH is the host material and compound 1 is the guest material. The mass ratio of GH to compound 1 is 100:8 and the thickness is 40 nanometers.

[0211] 6) Forming an electron transport layer: Electron transport materials ET and LiQ are deposited on the light-emitting layer by vacuum evaporation, with a mass ratio of 5:5 and a thickness of 30nm;

[0212] 7) Formation of electron injection layer: An electron injection layer LiQ with a thickness of 1 nm is vacuum-deposited on top of the electron transport layer;

[0213] 8) Forming a cathode layer: A cathode Al layer with a thickness of 100 nm is vacuum-deposited on top of the electron injection layer.

[0214] Device Examples 2-12

[0215] Except that the guest material of the luminescent layer is selected from the compounds shown in Table 1, all other conditions remain unchanged.

[0216] Device Comparison Example 1-2

[0217] The guest materials Ref-1 and Ref-2 of the OLED device replace compound 1 in device example 1, with other conditions remaining unchanged.

[0218] The current-voltage (JV) characteristics of the organic light-emitting diodes (OLEDs) in Examples 1-12 and Comparative Example 1 were tested using characterization equipment. Important parameters such as efficiency, lifetime, and external quantum efficiency were recorded. In Table 1, luminous efficiency is defined as a current density of 10 mA / cm². 2 The values ​​obtained are relative, and all luminous efficiency and lifetime are relative to the organic light-emitting diode of Comparative Example 1. It is evident that the efficiency and lifetime of the embodiments based on this application are significantly improved compared to the comparative example. The embodiments of this application use a silicon-containing organic compound with the general formula (1) as the main material of the light-emitting layer, while the comparative example uses other organic compounds as the main material of the light-emitting layer. Therefore, the OLED devices prepared based on the compounds of this application show significant improvements in both efficiency and lifetime.

[0219] Table 1

[0220]

[0221]

[0222] 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.

[0223] The embodiments described above are merely illustrative of several implementations 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 can be used to interpret the content of the claims.

Claims

1. A silicon-containing organic compound, characterized by, The structure is shown in general formula (1): wherein: X1, X2, X3 are independently selected from CR5 or N, and at least one of X1, X2 and X3 is selected from N; R1, R2 are selected from hydrogen or tert-butyl; R3, R4 are hydrogen; R5 is hydrogen; Ar1, Ar2 are independently selected from the following groups: ； * indicates the connecting position; X4 is independently selected from CR6 or N at each occurrence; Y1 is independently selected from CR7R8, NR9, O; R6 is H; R7, R8 are methyl; R9 is phenyl. n is selected from 1, 2, 3, 4 or 5; m is selected from 1, 2, 3 or 4.

2. The silicon-containing organic compound according to claim 1, characterized by The structure of the silicon-containing organic compound is shown in general formula (2-1) to (2-4): 。 3. The silicon-containing organic compound according to claim 1, wherein Ar1, Ar2 are independently selected from the following groups at each occurrence: ； wherein: * indicates the connecting position.

4. The silicon-containing organic compound according to claim 1, characterized by Ar1 is selected from the following groups: ； Ar2is selected from ; wherein, * indicates the connecting position; R6 is H; R7, R8 are methyl; R9 is phenyl.

5. A mixture characterized in that, The mixture comprises the silicon-containing organic compound according to any one of claims 1 to 4, and at least one organic functional material selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, an emitter, a host material or an organic dye.

6. A composition characterized in that, The composition comprises the silicon-containing organic compound according to any one of claims 1 to 4 or the mixture according to claim 5, and at least one organic solvent.

7. An organic electronic device, characterized in that The organic electronic device comprises the silicon-containing organic compound according to any one of claims 1 to 4, the mixture according to claim 5 or a functional layer prepared from the composition according to claim 6.

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