WO2023284654A1

WO2023284654A1 - Organic heterocyclic compound and application thereof in organic light emitting diode

Info

Publication number: WO2023284654A1
Application number: PCT/CN2022/104782
Authority: WO
Inventors: 谭甲辉; 陈怀俊; 潘君友
Original assignee: 浙江光昊光电科技有限公司
Priority date: 2021-07-10
Filing date: 2022-07-10
Publication date: 2023-01-19
Also published as: CN117529482A

Abstract

Provided are an organic heterocyclic compound and an application thereof in an organic light emitting diode. The organic compound has improved carrier balance and fluorescence quantum efficiency, and achieves high efficiency and long service life of an OLED device, and thus has massive application potential and application range. Additionally provided are a mixture, a composition and an organic electronic device comprising the organic compound.

Description

Organic Heterocyclic Compounds and Their Applications in Organic Light Emitting Diodes

technical field

The invention relates to the field of electroluminescent materials, in particular to an organic heterocyclic compound, a mixture and composition thereof, and its application in organic electronic devices, especially in organic electroluminescent devices. The invention also relates to an organic electronic component comprising the organic compound according to the invention, and to its use.

Background technique

Due to the diversity of organic semiconductor materials in terms of structure and synthesis, relatively low manufacturing cost, and their excellent optical and electrical properties, organic light-emitting diodes (OLEDs) have great potential in the application of optoelectronic devices (such as flat panel displays and lighting) .

The organic electroluminescence phenomenon refers to the phenomenon of converting electrical energy into light energy by using organic substances. An organic electroluminescence element utilizing the organic electroluminescence phenomenon generally has a positive electrode, a negative electrode, and a structure including an organic substance layer therebetween. In order to improve the efficiency and lifespan of the organic electroluminescence element, the organic layer has a multilayer structure, and each layer contains different organic substances. Specifically, it may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In this organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode to the organic layer, electrons are injected from the negative electrode to the organic layer, and excitons are formed when the injected holes and electrons meet. The excitons emit light when they transition back to the ground state. This organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

Both theory and experiment have proved that luminescent material is the most important factor to determine the efficiency of OLED devices. At present, the light-emitting layer of organic electroluminescent elements usually uses a mixed system of host/guest material as the light-emitting material, which can improve color purity, luminous efficiency and stability. In general, when using a host/guest material system, the choice of host material is very important, because the host material greatly affects the efficiency and stability of OLED devices. Preferably, the host material should have a suitable molecular weight for deposition under vacuum, and also need to have a high glass transition temperature and thermal decomposition temperature to ensure thermal stability, high electrochemical stability to ensure long service life, easy An amorphous film is formed, which has a good interfacial interaction with the adjacent functional layer materials, and molecular movement is not easy to occur.

Especially as a phosphorescent red host material, it is required that the material has good carrier transport ability and a suitable triplet energy level, so as to ensure that the energy can be effectively transferred to the guest material during the luminescence process, so as to achieve higher efficiency. The currently reported red light hosts are usually large conjugated system aromatic rings, such as fused ring carbazole derivatives reported in WO2012169821, WO2012165844, and WO2016013817. The compounds reported above have the problems of low device efficiency and poor stability, and at the same time ignore the problem of carrier transport balance of the host material in the device.

Therefore, further development of red-emitting phosphorescent host materials is needed to improve the efficiency and lifetime of OLED devices.

Contents of the invention

In view of the deficiencies in the prior art above, the object of the present invention is to provide an organic compound, a mixture thereof, a composition, an organic electronic device and an application thereof, aiming at solving the problems of the efficiency and lifetime of the existing OLED.

Technical scheme of the present invention is as follows:

A kind of organic compound, comprises the structure shown in general formula (I):

Wherein: ring A, ring B, ring C, ring D, ring E, ring F and ring G are the same or different and are independently selected from substituted or unsubstituted C ₆ -C ₃₀ aromatic rings, with 5-30 A heteroaromatic ring with 8 ring atoms or a condensed ring structural unit with 8-30 ring atoms, and the G ring can be none;

X is the same or different from each other independently selected from C or N;

Y is selected from BR ₁ , C(R ₁ R ₂ ), NR ₃ , Si(R ₁ R ₂ ), O or S, and each occurrence of R ₁ -R ₃ is independently selected from H, D, or has 1 to Straight-chain alkyl, alkoxy or thioalkoxy with 20 C atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy with 3 to 20 C atoms, or methyl Silyl groups, or keto groups with 1 to 20 C atoms, or alkoxycarbonyl groups with 2 to 20 C atoms, or aryloxycarbonyl groups with 7 to 20 C atoms, cyano, carbamoyl, Haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, _CF3 , Cl, Br, F, I, crosslinkable groups, or groups with 5 A substituted or unsubstituted aryl or heteroaromatic group of up to 60 ring atoms, or an aryloxy or heteroaryloxy group of 5 to 60 ring atoms, or _a combination of these groups; and R When -R ₃ is substituted, two adjacent carbon atoms in the same aromatic ring in the substituent can be fused to form a ring.

A high polymer comprises at least one repeating unit, and the repeating unit comprises a structural unit represented by general formula (I).

A mixture comprising an organic compound or polymer as described above, and at least one organic functional material, the organic functional material may be selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials material, electron blocking material, hole blocking material, emitter or host material.

A composition comprising an organic compound or high polymer or a mixture as described above, and at least one organic solvent.

An organic electronic device, comprising at least one organic compound or high polymer or mixture as described above.

Beneficial effects: According to the organic compound of the present invention, the large conjugated aromatic system is used to connect the nitrogen-absorbing electron-absorbing structural unit, and at the same time, it is matched with a suitable p-type material, which can further improve the carrier transport balance, significantly improve the device efficiency and prolong the device life. The organic compound according to the present invention can be used as a light-emitting layer material, and can improve its luminous efficiency and service life as an electroluminescent device by cooperating with other suitable materials, providing a light-emitting device with low manufacturing cost, high efficiency and long service life s solution.

detailed description

The present invention provides an organic compound and its application in an organic electroluminescent device. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

In the present invention, composition and printing ink, or ink have the same meaning, and they are interchangeable.

In the present invention, host material, host material, Host or Matrix material have the same meaning, and they can be interchanged.

In the present invention, "substituted" means that the hydrogen atom in the substituent is replaced by the substituent.

In the present invention, the "number of ring atoms" means the number of structural compounds (for example, monocyclic compounds, condensed ring compounds, crosslinked compounds, carbocyclic compounds, heterocyclic compounds) that constitute the ring itself in which atoms are bonded to form a ring. The number of atoms within an atom. When the ring is substituted by a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the carbazolyl group is 12.

In the embodiment of the present invention, the energy level structure of the organic material, the singlet energy level S1, the triplet energy level T1, HOMO, and LUMO play a key role. The determination of these energy levels is introduced below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (Ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating the energy levels of molecular orbitals.

The triplet energy level T1 of organic materials can be measured by low-temperature time-resolved luminescence spectroscopy; T1 and S1 can also be obtained by quantum simulation calculations (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), specifically The simulation method can be found in WO2011141110 or as described below in the examples. ΔE _ST is defined as (S1-T1).

It should be noted that the absolute values of HOMO, LUMO, S1, T1 depend on the measurement method or calculation method used, even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve can give different HOMO /LUMO value. Therefore, reasonably meaningful comparisons should be made with the same measurement methods and the same evaluation methods. In the description of the embodiments of the present invention, the values of HOMO, LUMO, S1, and T1 are based on Time-dependent DFT simulation, but do not affect the application of other measurement or calculation methods. ΔLUMO is defined as (LUMO+1)-LUMO, and ΔHOMO is defined as HOMO-(HOMO-1).

In the invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) is defined 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) is defined as the third lowest occupied orbital energy level, and so on.

The present invention provides a kind of organic compound as shown in general formula (I):

Wherein: ring A, ring B, ring C, ring D, ring E, ring F and ring G are the same or different and are independently selected from substituted or unsubstituted C ₆ -C ₃₀ aromatic rings, with 5-30 A heteroaromatic ring with 8-30 ring atoms or a condensed ring structure unit with 8-30 ring atoms; G ring can be none; X is the same or different and independently selected from C or N; Y is selected from BR ₁ , C(R ₁ R ₂ ), NR ₃ , Si(R ₁ R ₂ ), O or S, each occurrence of R ₁ -R ₃ is independently selected from H, D, or straight-chain alkyl having 1 to 20 C atoms , alkoxy or thioalkoxy, or branched or cyclic alkyl, alkoxy or thioalkoxy with 3 to 20 C atoms, or silyl, or 1 to 20 Keto with C atoms, or alkoxycarbonyl with 2 to 20 C atoms, or aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano group, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF ₃ , Cl, Br, F, I, crosslinkable groups, or substituted or unsubstituted groups with 5 to 60 ring atoms Substituted aromatic or heteroaromatic groups, or aryloxy or heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups; and when R ₁ -R ₃ are substituted, R ₁ In the substituent of _-R3 , adjacent two carbon atoms in the same aromatic ring can be fused to form a ring.

The aromatic ring group refers to a hydrocarbon group containing at least one aromatic ring. A heterocyclic aromatic ring group refers to an aromatic hydrocarbon group containing at least one heteroatom. A fused-ring aromatic group refers to an aromatic group whose ring can have two or more rings, in which two carbon atoms are shared by two adjacent rings, that is, a fused ring. A fused heterocyclic aromatic group refers to a fused ring aromatic hydrocarbon group comprising at least one heteroatom. For the purposes of the present invention, an aromatic group or a heterocyclic aromatic group includes not only aromatic ring systems but also nonaromatic ring systems. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. are also considered for the purpose of the invention is an aromatic group or a heterocyclic aromatic group. For the purposes of the present invention, fused-ring aromatic or heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which multiple aromatic or heteroaromatic groups can be divided by short Non-aromatic units are interrupted (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc. are likewise considered fused-ring aromatic ring systems for the purposes of this invention.

Specifically, examples of fused ring aromatic groups include: naphthalene, anthracene, fluoranthene, phenanthrene, phenalene, triphenylene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivative.

Specifically, examples of fused heterocyclic aromatic groups include: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran , thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primidine, quinazoline, quinazolinone , and its derivatives.

A straight-chain alkane group refers to an alkane in which the carbon atoms are connected in a single chain and are straight-chained. When the number of carbon atoms exceeds 3, the alkane chain can form a branched branched structure in addition to being connected in a straight chain, which is a branched alkane. When there are more than 3 carbon atoms, in addition to forming straight-chain or branched alkanes, carbon atoms can also be connected with single-chain or double bonds to form cyclic alkanes, which are alicyclic hydrocarbons. Alicyclic hydrocarbons can also contain more than two carbon rings, which can be connected in various ways: two rings in the molecule can share one carbon atom, and this system is called a spiro ring; carbon atoms can be used between two carbon atoms on the ring The bridge is connected to form a double-ring or polycyclic system, which is called a bridge ring; several rings can also be connected to each other to form a cage structure.

Specifically, examples of C ₁ -C ₈ linear alkane groups include: methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl.

Specifically, examples of C ₁ -C ₈ branched chain alkane groups are: isopropyl, tert-butyl, isopentane, neopentane, dimethylhexane, trimethylpropane, 2,3 dimethyl Butane, 2,2-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3- Dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, 2-methylheptane, 3-methylheptane, 4 -Methylheptane, 3-ethylhexane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane Hexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 2-methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,2 ,3-Trimethylpentane, 2,2,4-Trimethylpentane, 2,3,3-Trimethylpentane, 2,3,4-Trimethylpentane, 2,2,3 ,3-Tetramethylbutane, and its derivatives.

Specifically, examples of C ₃ -C ₈ alicyclic hydrocarbon groups are: cyclopropane, cyclobutane, methylcyclopropane, cyclopentane, cyclohexane, cycloheptane, 1,2-dimethylcyclopentane , 1-methyl-3-ethylcyclopentane, cyclooctane, cyclopentene, cyclooctyne, 1,3-cyclohexadiene, 1-methyl-1-cyclohexene, 3-methyl -1-cyclohexene, 3-methylcyclopentene, 1,6-dimethyl-1-cyclohexene, 5-methyl-1,3-cyclohexene, spiro[2.4]heptane, 5 - methylspiro[2.4]heptane, bicyclo[2.2.1]heptane, bicyclo[2.1.0]pentane, bicyclo[3.1.1]heptane, and derivatives thereof.

Alkoxy refers to the combination of alkyl and oxygen atoms. According to the type of alkyl, it can be further divided into branched or branched alkyl connected to oxygen, such as methoxy, ethoxy, propoxy, tert-butoxy Etc. and those linked by cycloalkane to oxygen, such as cyclopropoxy, cyclohexyloxy, etc.

Specifically, examples of C ₁ -C ₈ alkoxy groups include: methoxy, ethoxy, propoxy, 2-methylethoxy, cyclopropoxy, n-butoxy, tert-butoxy, Cyclobutoxy, 2-methylpropoxy, 3-methylpropoxy, n-pentyloxy, cyclopentyloxy, isopentyloxy, neopentyloxy, dimethylhexyloxy, trimethyl Propyloxy, n-hexyloxy, cyclohexyloxy, 2,3 dimethylbutoxy, 2,2 dimethylbutoxy, 2-methylhexyloxy, 3-methylhexyloxy, 2,2-dimethylpentyloxy, 3,3-dimethylpentyloxy, 2,3-dimethylpentyloxy, 2,4-dimethylpentyloxy, 3-ethylpentyloxy Base, n-heptyloxy, cycloheptyloxy, 2-methylheptyloxy, 3-methylheptyloxy, 4-methylheptyloxy, n-octyloxy, cyclooctyloxy, 3-ethyl Hexyloxy, 2,2-dimethylhexyloxy, 2,3-dimethylhexyloxy, 2,4-dimethylhexyloxy, 2,5-dimethylhexyloxy, 3, 3-Dimethylhexyloxy, 3,4-dimethylhexyloxy, 2-methyl-3-ethylpentyloxy, 3-methyl-3-ethylpentyloxy, and their derivatives .

In some preferred embodiments, the A ring, B ring, C ring, D ring, E ring, F ring and G ring in the organic compound are the same or different and are independently selected from substituted or unsubstituted Benzene ring, naphthalene, anthracene, phenanthrene, fluoranthene, pyrene, fluorene, pyrrole, furan, thiophene, pyridine, cyclopentadiene and dibenzofuran, etc., among which ring A, ring B, ring C, ring D and ring E There is at least one five-membered ring, and two adjacent rings can be fused, and the G ring means that it can be fused with the B ring to form a ring.

In certain embodiments, the G ring is none.

In some more preferred embodiments, ring A, ring B, ring C, ring D and ring E can be further selected from one or more combinations of the following structural groups, wherein the H on the ring can be optionally replace:

In some preferred embodiments, the structure of the organic compound is shown in general formula (II-a) or (II-b):

Wherein: X ₁ -X ₁₆ are the same or different, and are independently selected from CR ₄ or N, wherein R ₄ can be a substituted or unsubstituted C ₆ -C ₃₀ aromatic ring, heteroaromatic with 5-30 ring atoms Ring, fused ring with 8-30 ring atoms, C ₁ -C ₈ straight or branched alkanes, C ₃ -C ₁₀ alicyclic hydrocarbons, C ₁ -C ₈ alkoxy, where the substituent can be C ₆ -C ₃₀ aromatic ring, C ₅ -C ₃₀ heteroaromatic ring, C ₁₀ -C ₃₀ fused ring, C ₁ -C ₈ straight chain or branched alkanes, C ₃ -C ₁₀ alicyclic hydrocarbons, C ₁ -C ₈ alkanes Oxygen, allyl, cyano, halogen, hydrogen or deuterium, two adjacent R ₄ can be fused with each other to form a ring; the definition of Y is as above.

In some preferred embodiments, the core structure of the organic compound, that is, the general formula (I) or (II-a) or (II-b) except all substituents, is a ring atom number not greater than 45 The fused ring compound is preferably a fused ring compound with no more than 40 ring atoms, more preferably a fused ring compound with no more than 35 ring atoms, most preferably a fused ring structure with no more than 30 ring atoms.

In some more preferred embodiments, the structure of the organic compound is shown in general formula (III-a) or (III-b):

_Wherein : the definition of R is the same as that of R above, and the definition of Y is as above _.

In some preferred embodiments, when the above-mentioned R ₁ -R ₅ appear multiple times, they may be identically or differently selected from one of the following structural groups or a combination thereof:

Wherein: when V occurs multiple times, the same or different ones are independently selected from CR ₆ or N; when Q occurs multiple times, they are independently selected from BR ₇ , C(=O), C-(R ₇ R ₈ ), NR ₉ , O, S, P, P=O or P=S, wherein the definitions of R ₆ -R ₉ are the same as those of R ₁ above.

In some more preferred embodiments, the R ₁ -R ₅ can further be selected from one or more combinations of the following structural groups, wherein the H on the ring can be substituted arbitrarily:

where n1 is 1 or 2 or 3 or 4.

In some preferred embodiments, the substituents in the organic compound, such as R ₁ -R ₅ , can be connected to the aromatic ring through an L group, wherein the L group is selected from one or more of the following structures A combination of species, where the H on the ring can be substituted arbitrarily:

In some of the most preferred embodiments, the above-mentioned organic compound, wherein the L group can comprise the structure of the following chemical formula, wherein the H on the ring can be optionally substituted:

In some preferred embodiments, in the above-mentioned organic compound, the substituents R ₁ -R ₃ connected to Y may be an electron-withdrawing group or be substituted by an electron-withdrawing group. Suitable electron-withdrawing groups can be selected from F, cyano, or a combination of one or more of the following groups:

Among them: n is 1, 2 or 3; W is selected from CR ₁₀₁ or N, and at least one is N, and any two adjacent positions can form a monocyclic or polycyclic aliphatic or aromatic ring system; M ¹ , M ² and M ³ independently represent C(R ₁₀₂ R ₁₀₃ ), NR ₁₀₃ , Si(R ₁₀₃ R ₁₀₄ ), O, C=N(R ₁₀₅ ), C=C(R ₁₀₅ R ₁₀₆ ) or none ; R ₁₁ can be a substituted or unsubstituted C ₆ -C ₃₀ aromatic ring, a heteroaromatic ring with 5-30 ring atoms, a condensed ring with 8-30 ring atoms, C ₁ -C ₈ straight chain or branched Alkanes, C ₃ -C ₁₀ alicyclic hydrocarbons, C ₁ -C ₈ alkoxy groups, where the substituents of R ₁₁ can be C ₆ -C ₃₀ aromatic rings, C ₅ -C ₃₀ heteroaromatic rings, C ₁₀ -C ₃₀ fused ring, C ₁ -C ₈ straight chain or branched alkanes, C ₃ -C ₁₀ alicyclic hydrocarbons, C ₁ -C ₈ alkoxy, allyl, cyano, halogen, hydrogen or deuterium; R ₁₀₁ - The definition of R ₁₀₆ is the same as the definition of R ₁ above.

In other preferred embodiments, the above-mentioned organic compound, the electron-withdrawing group is selected from one or more combinations of the following groups:

In some preferred embodiments, the organic compound according to the present invention has a smaller singlet-triplet energy level difference, generally ΔE _st ≤ 0.3eV, preferably ΔE _st ≤ 0.2eV, more preferably ΔE _st ≤ 0.15eV, preferably ΔE _st ≤ 0.10eV.

Depending on the substitution pattern, organic compounds according to general formulas (III-a)-(III-b) can have various functions, including but not limited to hole transport function, electron transport function, light emitting function, exciton blocking function etc. Which compounds are particularly suitable for which functions are described in particular by the substituents R ₁ -R ₅ . The substituents R ₁ -R ₅ have an influence on the electronic properties of the units of the general formulas (III-a)-(III-b).

In a more preferred embodiment, according to the organic compound of the present invention, at least part of H is deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, very preferably 30% H is deuterated, preferably 40% of H is deuterated.

The specific structures of the organic compounds according to the present invention are listed below, but not limited thereto, and these structures can be substituted at all possible substitution positions.

The organic compound according to the present invention can be used as a functional material in electronic devices, especially in OLED devices. Organic functional materials can be divided into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM) , Emitter, host material (Host) and organic dyes.

In a preferred embodiment, the organic compounds according to the invention can be used as host materials or electron-transport materials or hole-transport materials.

In a preferred embodiment, the organic compounds according to the invention can be used as phosphorescent host materials or co-host materials.

As a phosphorescent host material, it must have an appropriate triplet energy level, namely T1. In some embodiments, the organic compound according to the present invention has T1≥2.2eV, preferably ≥2.4eV, more preferably ≥2.6eV, more preferably ≥2.65eV, most preferably ≥2.7eV.

Good thermal stability is desired as an organic functional material. Generally, the organic compounds according to the present invention have a glass transition temperature Tg ≥ 100°C. In a preferred embodiment, Tg≥120°C. In a more preferred embodiment, Tg≥140°C. In a more preferred embodiment, Tg≥160°C. In a most preferred embodiment, Tg≥180°C.

In some preferred embodiments, according to the organic compound of the present invention, its ((HOMO-(HOMO-1)) ≥ 0.2eV, preferably ≥ 0.25eV, more preferably ≥ 0.3eV, more preferably ≥ 0.35eV, very preferably ≥0.4eV, most preferably ≥0.45eV.

In other preferred embodiments, according to the organic compound of the present invention, its ((LUMO+1)-LUMO) ≥ 0.15eV, preferably ≥ 0.20eV, more preferably ≥ 0.25eV, more preferably ≥ 0.30 eV, preferably ≥ 0.35eV.

In some embodiments, the organic compound according to the present invention has a light-emitting function, and its light-emitting wavelength is between 300-1000 nm, preferably between 350-900 nm, more preferably between 400-800 nm. The luminescence referred to herein refers to photoluminescence or electroluminescence.

The present invention also relates to a high polymer, wherein at least one repeating unit contains the structure shown in general formula (I).

In some embodiments, the high polymer is a non-conjugated high polymer, wherein the structural unit represented by the general formula (I) is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤4000g/mol, preferably ≤3000g/mol, most preferably ≤2000g/mol.

High polymer, namely Polymer, includes homopolymer (homopolymer), copolymer (copolymer), block copolymer (block copolymer). In addition, in the present invention, high polymer also includes dendrimer (dendrimer), and the synthesis and application of dendrimer are please refer to 【Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed.George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

A conjugated polymer is a polymer whose main chain backbone is mainly composed of sp ² hybridized orbitals of C atoms. Famous examples include: polyacetylene and poly(phenylene vinylene). The C atoms in the chain can also be replaced by other non-C atoms, and when the ^sp2 hybridization on the main chain is interrupted by some natural defects, it is still considered as a conjugated polymer. In addition, the conjugated polymer in the present invention also includes aryl amine, aryl phosphine and other heterocyclic aromatic hydrocarbons (heteroarmatics), organometallic complexes (organometallic complexes) on the main chain. )Wait.

In a preferred embodiment, the polymer synthesis method is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the polymer according to the present invention has a glass transition temperature (Tg) ≥ 100°C, preferably ≥ 120°C, more preferably ≥ 140°C, more preferably ≥ 160°C, and most preferably ≥180°C.

In a preferred embodiment, according to the polymer of the present invention, the value range of its molecular weight distribution (PDI) is preferably 1-5, more preferably 1-4, more preferably 1-3, more preferably 1 ~2, most preferably 1~1.5.

In a preferred embodiment, according to the high polymer of the present invention, its weight average molecular weight (Mw) is preferably in the range of 10,000 to 1 million, more preferably 50,000 to 500,000, more preferably 100,000 to 400,000 10,000, more preferably 150,000 to 300,000, most preferably 200,000 to 250,000.

The invention also relates to a mixture comprising one of the above-mentioned organic compounds or polymers (H1) and at least one other organic functional material (H2). The organic functional materials include hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM), electron blocking material (EBM) , Organic host materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), organic thermally excited delayed fluorescent materials (TADF materials), especially light-emitting organometallic complexes. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein as a reference. Organic functional materials can be small molecules and polymer materials.

In a preferred embodiment, said mixture comprises at least one organic compound or polymer according to the present invention and one phosphorescent emitter. Here, the organic compound or high polymer according to the present invention can be used as the phosphorescent host material, wherein the weight percentage of the phosphorescent emitter is ≤20wt%, preferably ≤15wt%, more preferably ≤10wt%.

In another preferred embodiment, said mixture comprises at least one organic compound or polymer according to the present invention, a phosphorescent emitter and another host material (singlet or triplet host material) . In such an embodiment, the organic compound or high polymer according to the present invention can be used as auxiliary luminescent material, and its weight ratio to phosphorescent emitter is from 1:2 to 2:1. In another preferred embodiment, the organic compound or high polymer according to the present invention forms an exciplex with another host material, and the energy level of the exciplex is higher than that of the phosphorescent luminescence body.

In another preferred embodiment, said mixture comprises at least one organic compound or polymer according to the present invention, and one TADF material. Here, the organic compound or high polymer according to the present invention can be used as the host material of the TADF luminescent material, wherein the weight percentage of the TADF material is ≤15wt%, preferably ≤10wt%, more preferably ≤8wt%.

In other preferred embodiments, said mixture comprises an organic compound or polymer according to the present invention, and an HTM material.

In a very preferred embodiment, the mixture comprises an organic compound or polymer according to the invention and another host material (singlet or triplet host material). Here, the organic compound or high polymer according to the present invention can be used as the second host, and its weight percentage can be 30%-70%, preferably 40%-60%.

For detailed descriptions of host materials, phosphorescent emitter materials, HTM, fluorescent materials and TADF materials, see WO2018095395. The entire contents of this patent document are hereby incorporated by reference.

In a particularly preferred embodiment, the mixture comprises at least one organic compound or polymer (H1) according to the invention and another organic functional material (H2). Such a mixture can be used as a phosphorescent mixed host material, and can further include a phosphorescent emitter, wherein the weight percentage of the phosphorescent emitter is ≤20wt%, preferably ≤15wt%, more preferably ≤10wt%.

The following is a detailed description of the mixture comprising the organic compound or high polymer (H1) of the present invention and another organic functional material (H2) as a phosphorescent mixed host material.

In a preferred embodiment, said another organic functional material (H2) has hole transport properties.

More preferably, the other organic functional material (H2) has electron transport properties as well as hole transport properties.

Generally, the molar ratio of the organic compound or polymer (H1) of the present invention to another organic functional material (H2) ranges from 1:9 to 9:1.

Preferably, the molar ratio of the organic compound or polymer (H1) of the present invention to another organic functional material (H2) ranges from 3:7 to 7:3.

More preferably, the molar ratio of the organic compound or polymer (H1) of the present invention to another organic functional material (H2) ranges from 4:6 to 6:4.

Optimally, the molar ratio of the organic compound or polymer (H1) of the present invention to another organic functional material (H2) is 5:5.

In a preferred embodiment, said a mixture, another organic functional material (H2) is selected from compounds represented by the following general formula (IV):

Wherein: A is selected from substituted or unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups with 5-100 ring atoms; D is an electron-rich group; p is any integer of 1-6.

In some preferred embodiments, the electron-rich (or electron-donating) group D in the general formula (IV) includes any of the following groups:

in:

Ar1 represents an aromatic group or a heteroaromatic group with ring atoms of 5-40;

Z ¹ , Z ² , and Z ³ independently represent a single bond, C-(R ₂₀₁ )2, NR ₂₀₂ , Si-(R ₂₀₃ )2, O, C(=O), S or S=O, but Z ² Unlike Z ³ , it is a single bond at the same time;

The definitions of R ⁴ and R ⁵ are the same as those of R ₄ above, and the definitions of R ₂₀₁ -R ₂₀₃ are the same as those of R ₁ above.

In some more preferred embodiments, the electron-rich (or electron-donating) group D in the general formula (IV) includes any of the following groups:

Wherein R ⁴ is as defined above.

In some preferred embodiments, p is 1 or 2 or 3 or 4; in more preferred embodiments, p is 1 or 2 or 3; in the most preferred embodiments, p is 1 or 2.

In some preferred embodiments, according to the mixture of the present invention, another organic functional material (H2) is selected from one of the following structural formulas:

Wherein, the meaning of A is as above, and the meaning of Ar2 is the same as that of Ar1.

In some embodiments, in the mixture according to the present invention, H1 or H2 has a higher triplet energy level T1, generally T1≥2.2eV, preferably T1≥2.3eV, more preferably T1≥2.4eV, more preferably More preferably, T1≥2.5eV, most optimally, T1≥2.6eV.

In some preferred embodiments, the organic mixture, wherein H1 and H2 form a type II heterojunction structure, that is, the highest occupied orbital energy level (HOMO) of H1 is lower than the HOMO of H2, and the lowest unoccupied orbital of H1 The energy level (LUMO) is lower than that of H2.

In a more preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(T1(H1),T1(H2)) +0.1eV, where LUMO(H1), HOMO(H1) and T1(H1) are the lowest unoccupied orbital, highest occupied orbital and triplet energy level of H1 respectively, LUMO(H2), HOMO(H2) and T1( H2) are the lowest unoccupied orbital, the highest occupied orbital, and the energy level of the triplet state of H2, respectively.

In a preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(T1(H1),T1(H2));

In a more preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(T1(H1), T1(H2)) -0.05eV;

In a more preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(T1(H1),T1(H2) )-0.1eV;

In a very preferred embodiment, said mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(T1(H1),T1(H2)) -0.15eV;

In a most preferred embodiment, said mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(T1(H1),T1(H2)) -0.2eV.

Below is an example according to another kind of organic functional material (H2) shown in general formula (IV) Specific example, but not limited to:

In a more preferred embodiment, according to the mixture of the present invention, wherein at least one of H1 and H2, preferably H1, its ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, more preferably Preferably ≥0.20eV, more preferably ≥0.25eV, most preferably ≥0.30eV.

In another more preferred embodiment, according to the mixture of the present invention, wherein at least one of H1 and H2, preferably H2, its (HOMO-(HOMO-1)) ≥ 0.2eV, preferably ≥ 0.25eV, More preferably ≥0.30eV, more preferably ≥0.35eV, most preferably ≥0.40eV.

One object of the present invention is to provide a material solution for evaporation-type OLEDs.

In a preferred embodiment, the mixtures according to the invention are used in vapor-depositable OLED devices. For this purpose, H1 and H2 in the organic compound or mixture according to the present invention have a molecular weight of ≤ 1000 g/mol, preferably ≤ 900 g/mol, very preferably ≤ 850 g/mol, more preferably ≤ 800 g/mol, most preferably ≤ 700 g /mol.

In a preferred embodiment, the mixture, wherein the molecular weight difference between H1 and H2 does not exceed 100 Dalton; preferably the molecular weight difference does not exceed 60 Dalton; more preferably the molecular weight difference does not exceed 30 Dalton.

In another preferred embodiment, the mixture, wherein the difference between the sublimation temperatures of H1 and H2 does not exceed 30K; preferably the difference between the sublimation temperatures does not exceed 20K; more preferably the difference between the sublimation temperatures does not exceed 10K.

Another object of the present invention is to provide a material solution for printing OLEDs.

For this purpose, at least one, preferably both, of H1 and H2 in the organic compound or mixture according to the invention has a molecular weight of ≥ 700 g/mol, preferably ≥ 800 g/mol, very preferably ≥ 900 g/mol, More preferably > 1000 g/mol, most preferably > 1100 g/mol.

In the co-host in the form of Premix in the vapor-deposited OLED, the two host materials are required to have similar chemical or physical properties, such as molecular weight and sublimation temperature. In solution-processed OLEDs, two host materials with different properties may enhance the film-forming properties and thus enhance the device performance. The stated properties may be other than molecular weight, sublimation temperature, eg glass transition temperature, different molecular volumes, etc. Thereby printing OLED, according to the preferred embodiment of the mixture of the present invention has one of the following or the combination of two or more thereof:

1) The molecular weight difference between H1 and H2 is ≥120 g/mol, preferably ≥140 g/mol, more preferably ≥160 g/mol, most preferably ≥180 g/mol.

2) The difference between the sublimation temperatures of H1 and H2 is ≥60K, preferably ≥70K, more preferably ≥75K, most preferably ≥80K.

3) The difference between the glass transition temperatures of H1 and H2 is ≥20K, preferably ≥30K, more preferably ≥40K, most preferably ≥45K.

4) The molecular volume difference between H1 and H2 is ≥20%, preferably ≥30%, more preferably ≥40%, most preferably ≥45%.

In other embodiments, at least one of H1 and H2 in the organic compound or mixture according to the present invention, preferably both, have a solubility in toluene of ≥ 2 mg/mL, preferably ≥ 3 mg at 25 °C /mL, more preferably ≥ 4mg/mL, most preferably ≥ 5mg/mL.

In a preferred embodiment, the mixture, wherein the molar ratio of H1 and H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; the more preferred molar ratio is 4 :6 to 6:4.

In some other embodiments, the organic compound according to the present invention has a solubility in toluene at 25°C of ≥10 mg/mL, preferably ≥15 mg/mL, most preferably ≥20 mg/mL.

The invention still further relates to a composition or ink comprising an organic compound or polymer according to the invention and at least one organic solvent.

When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of suitable inks are tailored to the specific substrate and specific printing method.

In a preferred embodiment, the ink of the present invention has a surface tension of about 19 dyne/cm to 50 dyne/cm at working temperature or at 25° C., more preferably 22 dyne/cm to 35 dyne/cm, most preferably It is in the range of 25dyne/cm to 33dyne/cm.

In another preferred embodiment, the viscosity of the ink according to the present invention is in the range of 1 cps to 100 cps at working temperature or 25° C., preferably in the range of 1 cps to 50 cps, more preferably in the range of 1.5 cps to 20 cps, most preferably The best is in the range of 4.0cps to 20cps. Compositions so formulated will facilitate inkjet printing.

Viscosity can be adjusted by different methods, such as by suitable solvent selection and concentration of functional materials in the ink. The ink containing the organic compound according to the present invention can facilitate people to adjust the printing ink in an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition of the present invention is in the range of 0.3% to 30wt%, preferably in the range of 0.5% to 20wt%, more preferably in the range of 0.5% to 15wt%, more preferably It is in the range of 0.5% to 10wt%, preferably in the range of 1% to 5wt%.

In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, especially aliphatic chain/ring substituted aromatic solvents, or aromatic ketone solvents , or aromatic ether solvents.

Examples of solvents suitable for the present invention are, but are not limited to: Aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentabenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Basenaphthalene, 3-isopropylbiphenyl, p-methylcumene, pentapentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, di Hexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene , diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropane base) pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetralin Ketones, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives substances, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, different ketone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, fo ketone, di-n-amyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy -2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethyl Oxytoluene, 4-ethyl ethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, Glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethyl ether 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 ;Ester Solvent: Alkyl Caprylate, Alkyl Sebacate, Alkyl Stearate, Alkyl Benzoate, Alkyl Phenylacetate, Alkyl Cinnamate, Alkyl Oxalate, Alkyl Maleate, Alkyl Lactone, Oil Alkyl esters, etc.

Further, according to the ink of the present invention, the at least one solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5- Hexandione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl 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.

In other embodiments, the printing ink further contains another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, 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 , decalin, indene and/or mixtures thereof.

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

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

The composition in the embodiment of the present invention may include 0.01 to 20 wt % of the organic compound or its mixture according to the present invention, preferably 0.1 to 15 wt %, more preferably 0.2 to 10 wt %, most preferably 0.25 to 5% by weight of organic compounds or mixtures thereof.

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

Among them, suitable printing or coating techniques include (but are not limited to) inkjet printing, jet printing (Nozzle Printing), letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, reverse roller Printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot die coating, etc. Preferred are inkjet printing, jet printing and gravure printing. The solution or suspension may additionally include one or more components such as surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, binders, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information about printing technology and its requirements for related solutions, such as solvent and concentration, viscosity, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" (Handbook of Print Media: Technologies and Production Methods) edited by Helmut Kipphan, ISBN 3-540-67326-1.

Based on the above-mentioned organic compound, the present invention also provides an application of the above-mentioned organic compound or high polymer, that is, the application of the organic compound or high polymer to an organic electronic device, and the organic electronic device can be selected from, but not Limited to, organic light-emitting diodes (OLED), organic photovoltaic cells (OPV), organic light-emitting cells (OLEEC), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors and organic Plasmon Emitting Diode (Organic Plasmon Emitting Diode), etc., are particularly preferably organic electroluminescent devices, such as OLED, OLEEC, organic light emitting field effect tube. In the embodiment of the present invention, the organic compound is preferably used in the light-emitting layer of the electroluminescence device.

The present invention further relates to an organic electronic device comprising at least one organic compound or polymer as described above. Generally, such an organic electronic device at least comprises a cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one organic compound or high polymer as mentioned above. The organic electronic device can be selected from, but not limited to, organic light emitting diode (OLED), organic photovoltaic cell (OPV), organic light emitting cell (OLEEC), organic field effect transistor (OFET), organic light emitting field effect transistor, organic laser , organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferably organic electroluminescent devices, such as OLED, OLEEC, organic light emitting field effect tube.

In some particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer, the light-emitting layer comprises a kind of said organic compound or high polymer, or comprises a kind of said organic compound or high polymer and A phosphorescent emitter, or comprises a kind of said organic compound or high polymer and a kind of host material, or comprises a kind of said organic compound or high polymer, a kind of phosphorescent emitter and a kind of host material.

In the electroluminescent device mentioned above, especially OLED, it includes a substrate, an anode, at least one light-emitting layer, and a cathode.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. See, eg, 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. Substrates free of surface defects are particularly desirable. In a preferred embodiment, the substrate is flexible and can be selected from polymer film or plastic, and its glass transition temperature Tg is above 150°C, preferably above 200°C, more preferably above 250°C, most preferably over 300°C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the emitter in the light emitting layer or the HOMO energy level or the valence band energy level of the p-type semiconductor material as HIL or HTL or electron blocking layer (EBL) It is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. 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), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill 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), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to fabricate devices according to the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the emissive layer. In a preferred embodiment, the work function of the cathode and the LUMO energy level of the luminescent body in the light-emitting layer or as the n-type semiconductor material of the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) Or the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices according to the invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, _LiF /Al, MgAg alloys, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material may 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), and the like.

OLEDs can also contain other functional layers such as hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), hole blocking layer (HBL). Materials suitable for these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these three patent documents are hereby incorporated herein by reference.

In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer thereof is prepared from the composition according to the present invention.

According to the light-emitting device of the present invention, its light-emitting wavelength is between 300-1000nm, preferably between 350-900nm, more preferably between 400-800nm.

The present invention also relates to the application of the organic electronic device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors and the like.

The present invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., incorporating organic electronic devices according to the present invention.

The present invention will be described below in conjunction with preferred embodiment, but the present invention is not limited to following embodiment, it should be understood that appended claims have summarized the scope of the present invention, those skilled in the art should understand under the guidance of the present invention concept It is recognized that certain 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.

Example 1

Under nitrogen atmosphere, 1-bromocarbazole (100g, 632mmol), o-nitrophenylboronic acid (105.5g, 632mmol), tetrakis (triphenylphosphine) palladium (36.5g, 31.6mmol), cesium carbonate (205.9g , 632mmol) into a 2000mL dry and clean three-neck flask, inject 1000mL of tetrahydrofuran/water mixed solvent (THF:H2O=10:1), vacuumize and inflate with nitrogen for five times, then raise the temperature to 110°C and stir for 12h. After the reaction was complete, the solvent was removed by rotary evaporation, extracted three times with dichloromethane and saturated brine, and the organic phases were combined, dried, filtered and separated by silica gel column chromatography (dichloromethane:petroleum ether=5:1) to obtain intermediate 1a, 23 g, 83% yield.

Under nitrogen atmosphere, intermediate 1a (80g, 277mmol), 1,8-dibromonaphthalene (79.3g, 277mmol), sodium tert-butoxide (31.9g, 332.4mmol), tri-tert-butylphosphine (67.3g, 332.4mmol) into a 1000mL dry and clean three-neck flask, inject 500mL of dry toluene, vacuumize and fill with nitrogen for five cycles, then raise the temperature to 110°C and stir for 12h. After the reaction was complete, the solvent was removed by rotary evaporation, extracted three times with dichloromethane and saturated brine, and the organic phases were combined, dried, filtered and separated by silica gel column chromatography (dichloromethane:petroleum ether=5:1) to obtain intermediate 1b, 23 g, 83% yield.

Under nitrogen atmosphere, intermediate 1b (30g, 60.8mmol), cesium carbonate (19.8g, 60.8mmol), bis(tricyclohexylphosphine) palladium dichloride (11.9g, 15.2mmol), pivalic acid (70mL , 60.8mmol) into a 500mL dry and clean three-neck flask, inject 200mL of dry toluene, vacuumize and fill with nitrogen for five cycles, then raise the temperature to 110°C and stir for 12h. After the reaction was complete, the solvent was removed by rotary evaporation, extracted three times with dichloromethane and saturated brine, and the organic phases were combined, dried, filtered and separated by silica gel column chromatography (dichloromethane:petroleum ether=5:1) to obtain intermediate 1c, 23 g, 83% yield.

Under a nitrogen atmosphere, add intermediate 1c (18g, 43.6mmol) and triethoxyphosphorus (5.8g, 43.6mmol) into a 500mL dry and clean three-neck flask, vacuumize and nitrogen cycle five times, then heat up to 110°C and stir Reaction 12h. After the reaction was complete, the solvent was removed by rotary evaporation, extracted three times with dichloromethane and saturated brine, and the organic phases were combined, dried, filtered and separated by silica gel column chromatography (dichloromethane:petroleum ether=5:1) to obtain intermediate 1d, 23 g, 83% yield.

Under nitrogen atmosphere, intermediate 1d (8.7g, 22.8mmol), compound 1e (8.2g, 22.8mmol), tridibenzylideneacetone dipalladium (1.04g, 1.14mmol) and sodium tert-butoxide (2.63g , 27.4mmol) into a 500mL three-necked flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (4.6g, 22.8mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:20) gave 7.79g of solid powder with a yield of 58.6%.

Example 2

Under nitrogen atmosphere, intermediate 1d (8.7g, 22.8mmol), compound 2a (8.2g, 22.7mmol), tridibenzylideneacetone dipalladium (1.04g, 1.14mmol) and sodium tert-butoxide (2.63g , 27.4mmol) into a 500mL three-necked flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (4.6g, 22.8mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:20) gave 8.24g of solid powder with a yield of 62%.

Example 3

Under nitrogen atmosphere, intermediate 1d (12.4g, 32.6mmol), compound 3a (12.7g, 32.6mmol), tridibenzylideneacetone dipalladium (1.5g, 1.63mmol) and sodium tert-butoxide (3.76g , 39.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (6.6g, 32.6mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:16) gave 11.06g of solid powder with a yield of 55.2%.

Example 4

Under nitrogen atmosphere, intermediate 1d (9.9g, 26.1mmol), compound 4a (8.5g, 26.1mmol), tridibenzylideneacetone dipalladium (1.2g, 1.3mmol) and sodium tert-butoxide (2.5g , 26.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (5.28g, 26.1mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10) gave 8.1 g of solid powder with a yield of 54.7%.

Example 5

Under nitrogen atmosphere, intermediate 1d (9.9g, 26.1mmol), compound 5a (8.9g, 26.1mmol), tridibenzylideneacetone dipalladium (1.2g, 1.3mmol) and sodium tert-butoxide (2.5g , 26.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (5.28g, 26.1mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10) gave 9.3g of solid powder with a yield of 62.9%.

Example 6

Under nitrogen atmosphere, compound 6a (18.0g, 51.9mmol), compound 6b (8.9g, 51.9mmol), tetrakis (triphenylphosphine) palladium (0.6g, 0.52mmol) and X-Phos (0.6g, 1.3 mmol) into a 500mL three-neck flask in turn, then inject 200mL of toluene into the flask and vacuumize nitrogen for three times, and finally, slowly drop 50mL of aqueous solution dissolved in potassium phosphate (13.2g, 62.3mmol) into the flask, and heat to 110°C The reaction was refluxed for 8 hours, the solvent was removed by rotary evaporation and extracted three times with dichloromethane and deionized water. The combined organic phases were separated and purified by silica gel column chromatography (petroleum ether as eluent) to obtain 16.8 g of intermediate 6c with a yield of 72.6%.

Under nitrogen atmosphere, intermediate 1d (15.4g, 40.6mmol), intermediate 6c (16g, 40.6mmol), tridibenzylideneacetone dipalladium (1.86g, 2.03mmol) and sodium tert-butoxide (4.68g , 48.7mmol) were successively added into a 500mL three-necked flask, then 200mL of dry toluene was injected into the flask and evacuated for nitrogen replacement three times, and finally tri-tert-butylphosphine (8.2g, 40.6mmol) was slowly added dropwise into the flask and heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane: petroleum ether = 1:20) gave 18.9 g of solid powder with a yield of 70.3%.

Example 7

Add 1-bromocarbazole (100g, 457mmol), 1-chloro-2-bromo-3-nitrobenzene (80g, 457mmol) into a 2000mL dry and clean three-necked flask, and simultaneously add tetrakistriphenylphosphine palladium (10g), cesium carbonate 60g, tetrahydrofuran and water (1000ml: 200ml). After five cycles of vacuum pumping and nitrogen filling, the temperature was raised to 75° C. and the reaction was stirred and refluxed for 12 hours. Cool down to room temperature, pass through a short column of silica gel, spin dry, and separate by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid, which is vacuum-dried at 60°C to obtain 120.6g of product 7a.

In a 1000 mL dry and clean three-neck flask, add intermediate 7a (50 g, 186 mmol), 500 mL of toluene, 1 bromocarbazole (38 g, 190 mmol), 20 g of sodium tert-butoxide, and 15 g of tri-tert-butylphosphine. After five cycles of vacuum pumping and nitrogen filling, the temperature was raised to 100° C. and the reaction was stirred and refluxed for 12 hours. The temperature was lowered to room temperature, passed through a short column of silica gel, spin-dried, extracted with ethyl acetate water and separated by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid, which was vacuum-dried at 60°C to obtain 30.4g of product 7b.

In a dry and clean 500mL three-neck flask, add intermediate 7b (20g, 46mmol) and 40g of triethylphosphine, replace with nitrogen for 4-5 times, heat up to 100°C and start stirring for 24h. After concentration, ethyl acetate and saturated aqueous sodium chloride were added to extract three times, and then separated by column chromatography (ethyl acetate: petroleum ether 15:1) to obtain 12.3 g of 7c as a light yellow solid.

In a 500 mL dry and clean three-necked flask, add intermediate 7c (10 g, 21 mmol), 200 mL of toluene, 4 g of sodium tert-butoxide, 3 g of tri-tert-butylphosphine, and 200 ml of toluene. After five cycles of vacuum pumping and nitrogen filling, the temperature was raised to 100° C. and the reaction was stirred and refluxed for 12 hours. Cool down to room temperature, pass through a short column of silica gel, spin dry, extract with ethyl acetate water, and separate by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid, which was vacuum-dried at 60°C to obtain 8.2 g of product 7d.

Under nitrogen atmosphere, intermediate 7d (8g, 18mmol), compound 1e (8.3g, 18mmol), tridibenzylideneacetone dipalladium (1.04g, 1.14mmol) and sodium tert-butoxide (2.63g, 27.4mmol ) into a 500mL three-neck flask in turn, then inject 220mL of dry toluene into the flask and vacuumize nitrogen for three times, and finally tri-tert-butylphosphine (4.6g, 22.8mmol) is slowly added dropwise into the flask, heated to 110°C under reflux React for 12 hours. After the reaction is completed, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline. The combined organic phase is passed through a silica gel column. Chromatographic separation and purification (eluent dichloromethane:petroleum ether=1:20) gave 7.5g of solid powder Comp-7 with a yield of 72.6%.

Example 8

Under nitrogen atmosphere, intermediate 7d (9.6g, 22.8mmol), compound 2a (8.2g, 22.7mmol), tridibenzylideneacetone dipalladium (1.04g, 1.14mmol) and sodium tert-butoxide (2.63g , 27.4mmol) into a 500mL three-necked flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (4.6g, 22.8mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:20) gave 8.24g of solid powder with a yield of 62%.

Example 9

Under nitrogen atmosphere, intermediate 7d (9.6g, 32.6mmol), compound 3a (12.7g, 32.6mmol), tridibenzylideneacetone dipalladium (1.5g, 1.63mmol) and sodium tert-butoxide (3.76g , 39.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (6.6g, 32.6mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:16) gave 11.06g of solid powder with a yield of 55.2%.

Example 10

Under nitrogen atmosphere, intermediate 7d (10.9g, 26.1mmol), compound 4a (8.5g, 26.1mmol), tridibenzylideneacetone dipalladium (1.2g, 1.3mmol) and sodium tert-butoxide (2.5g , 26.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (5.28g, 26.1mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10) gave 8.1 g of solid powder with a yield of 54.7%.

Example 11

Under nitrogen atmosphere, intermediate 7d (10.9g, 26.1mmol), compound 5a (8.9g, 26.1mmol), tridibenzylideneacetone dipalladium (1.2g, 1.3mmol) and sodium tert-butoxide (2.5g , 26.1mmol) into a 500mL three-neck flask in turn, then inject 200mL of dry toluene into the flask and vacuum nitrogen replacement three times, finally tri-tert-butylphosphine (5.28g, 26.1mmol) was slowly added dropwise into the flask, heated to Reflux reaction at 110°C for 12 hours. After the reaction, pour the reaction mixture into 500mL deionized water and stir rapidly. During this period, the product is continuously precipitated. After suction filtration, the product is dissolved again with dichloromethane and extracted three times with saturated saline, and the organic phases are combined. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10) gave 9.3g of solid powder with a yield of 62.9%.

Example 12

Under nitrogen atmosphere, Intermediate 7d (17g, 40.6mmol), Intermediate 6c (16g, 40.6mmol), tridibenzylideneacetone dipalladium (1.86g, 2.03mmol) and sodium tert-butoxide (4.68g, 48.7mmol) into a 500mL three-necked flask in turn, then inject 200mL of dry toluene into the flask and vacuumize nitrogen for three times, finally tri-tert-butylphosphine (8.2g, 40.6mmol) was slowly added dropwise into the flask, heated to 110 ℃ reflux reaction for 12h. After the reaction was completed, the reaction mixture was poured into 500mL deionized water and stirred rapidly. During this period, the product was continuously precipitated. After suction filtration, the product was dissolved again with dichloromethane and extracted three times with saturated saline. Separation and purification by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:20) gave 18.9g of solid powder with a yield of 70.3%.

Example 13

Under nitrogen atmosphere, compound 8a (20.2g, 50mmol), compound 8b (17.2g, 100mmol), tetrakis (triphenylphosphine) palladium (3.5g, 3mmol), tetrabutylammonium bromide (8.1g, 25mmol) and sodium hydroxide (4g, 100mmol) into a 500mL three-necked flask in turn, then 200mL of toluene and 50mL of deionized water were added, vacuumed and replaced by nitrogen three times, heated at 110°C and stirred for 24 hours to complete the reaction, and the reaction solution was rotary evaporated Most of the solvent was removed, washed three times with dichloromethane dissolved in water, and the combined organic phase was separated and purified by silica gel column chromatography (petroleum ether as eluent) to obtain 18.7 g of intermediate 8c with a yield of 75%.

Add (14.9g, 30mmol) intermediate 8c and 100mL N,N-dimethylformamide into a 250mL single-necked flask, add 30mmol NBS N,N-dimethylformamide solution dropwise under ice bath, and stir the reaction in the dark After 12 hours, the reaction was completed, and the reaction solution was poured into 300 mL of water, filtered with suction, and the filter residue was recrystallized to obtain 17.3 g of intermediate 8d, with a yield of 90%.

Under a nitrogen atmosphere, intermediate Intermediate 8d (34.4 g, 20 mmol), intermediate compound 8e (11.5 g, 20 mmol), tetrakis(triphenylphosphine)palladium (0.7 g, 0.6 mmol) and tetrabutyl bromide Ammonium (3.2g, 10mmol) and sodium hydroxide (1.6g, 40mmol) were sequentially added to a 500mL three-necked flask, and then 200mL of toluene and 50mL of deionized water were injected into the flask, vacuumed and replaced with nitrogen three times, and heated to 110°C for 12h under reflux. After the reaction was completed, the solvent was removed by rotary evaporation, and then the product was dissolved with dichloromethane and extracted three times with saturated brine, and the combined organic phase was separated and purified by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10), 18.7 g of solid powder was obtained, yield 85%.

Example 14

Under nitrogen atmosphere, intermediate 8d (11.5g, 20mmol), compound 9a (44.4g, 20mmol), tetrakis(triphenylphosphine) palladium (0.7g, 0.6mmol), tetrabutylammonium bromide (3.2g, 10mmol), sodium hydroxide (1.6g, 40mmol), (10mL) water, and (80mL) toluene were added into a 250mL three-necked flask, heated at 110°C and stirred for 12 hours to complete the reaction. Dichloromethane was dissolved and washed three times with water, and the combined organic phases were separated and purified by silica gel column chromatography (eluent dichloromethane:petroleum ether=1:10) to obtain 21.8 g of solid powder with a yield of 85%.

The energy levels of organic compound materials can be obtained through quantum calculations, such as using TD-DFT (time-dependent density functional theory) through Gaussian09W (Gaussian Inc.). For specific simulation methods, please refer to WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of organic molecules is determined by the TD-DFT (time-dependent density functional theory) method Calculate "TD-SCF/DFT/Default Spin/B3PW91" and the basis set "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO energy levels are calculated according to the calibration formula below, and S1, T1 and resonance factor f(S ₁ ) are used directly.

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

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

Among them, HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1:

Table I

Fabrication and Measurement of OLED Devices

The preparation process of the above-mentioned OLED device is described in detail through specific examples below. The structure of the red OLED device is: ITO/HI/HI-1/HT-2/EML/ET:Liq/Liq/Al.

The preparation steps are as follows:

a. Cleaning of ITO (indium tin oxide) conductive glass substrate: use various solvents (such as one or more in chloroform, acetone or isopropanol) to clean, and then perform ultraviolet ozone treatment;

b. HI (30nm), HT-1 (60nm), HT-2 (10nm), host material: 3% RD (40nm), ET: Liq (50:50; 30nm), Liq (1nm), Al (100nm ) in high vacuum (1×10 ^-6 mbar) by thermal evaporation; move the ITO substrate into the vacuum vapor deposition equipment, and use resistance heating evaporation source under high vacuum (1×10 ^-6 mbar) An HI layer with a thickness of 30 nm is formed, and a 60 nm HT-1 layer and a 10 nm HT-2 layer are sequentially heated on the HI layer. Then comp-1 was placed in one evaporation unit, and compound RD was placed in another evaporation unit as a guest, so that the materials were vaporized at different rates, so that the weight ratio of comp-1:Dopant was 100:3, and in the hole transport layer A luminescent layer of 40 nm was formed on it. Next, ET and LiQ were placed in different evaporation units, so that they were co-deposited at a ratio of 50% by weight to form a 30nm electron transport layer on the light-emitting layer, and then 1nm LiQ was deposited on the electron transport layer as an electron injection layer. , finally depositing an Al cathode with a thickness of 100 nm on the electron injection layer;

c. Encapsulation: The device is encapsulated with ultraviolet curable resin in a nitrogen glove box.

The implementation method of device embodiment 2-device embodiment 7 is the same as that of device embodiment 1. Except replacing comp-1 with comp-2, comp-4 and different co-principals. The co-host means that the two compounds are respectively placed in different evaporation units to control the weight ratio of the materials.

The current-voltage and luminescence (IVL) characteristics of red OLED devices are characterized by characterization equipment, and important parameters such as efficiency, lifetime and driving voltage are recorded at the same time. The performance of the red OLED devices is summarized in Table 2. where the lifetimes are values relative to the comparative scale.

Table 2

After testing, compared with Comparative Example 1, the luminous efficiency and lifetime of Device Example 1-Device Example 9 are significantly improved. It can be seen that the luminous efficiency and lifespan of the OLED device prepared by using the organic compound of the present invention are greatly improved. Device Example 10-Device Example 17 Using the organic compound of the present invention together with other materials with hole transport capability can improve the carrier balance, and further improve the luminous efficiency and lifetime of the device.

It should be understood that the application of the present invention is not limited to the above examples, and those skilled in the art can make improvements or transformations according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.

Claims

A kind of organic compound, comprises the structure represented as general formula (I):

in:

A ring, B ring, C ring, D ring, E ring, F ring and G ring are the same or different and independently selected from substituted or unsubstituted C 6 -C 30 aromatic rings, with 5 to 30 rings atom heteroaromatic ring or condensed ring structural unit with 8 to 30 ring atoms, G ring can be none;

X is the same or different from each other independently selected from C or N;

Y is selected from BR 1 , C(R 1 R 2 ), NR 3 , Si(R 1 R 2 ), O or S;

Each occurrence of R 1 -R 3 is independently selected from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a group having 3 to 20 C atoms Branched or cyclic alkyl, alkoxy or thioalkoxy groups, or silyl groups, or keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or aryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF 3 , Cl, Br, F, I, crosslinkable groups, or substituted or unsubstituted aromatic or heteroaromatic groups with 5 to 60 ring atoms, or substituted or unsubstituted aromatic groups with 5 to 60 ring atoms Aryloxy or heteroaryloxy groups, or a combination of these groups; and when R 1 -R 3 are substituted, two adjacent carbon atoms in the same aromatic ring in the substituents can be fused to form a ring.
The organic compound according to claim 1, wherein A ring, B ring, C ring, D ring, E ring, F ring and G ring are identical or different and are independently selected from substituted or unsubstituted benzene rings, Naphthalene, anthracene, phenanthrene, fluoranthene, pyrene, fluorene, pyrrole, furan, thiophene, pyridine, cyclopentadiene and dibenzofuran, etc., wherein there are at least A five-membered ring.
The organic compound according to claim 1, has the structure shown in general formula (II-a) or (II-b):

in:

X 1 -X 16 are the same or different, and are independently selected from CR 4 or N, wherein R 4 can be a substituted or unsubstituted C 6 -C 30 aromatic ring, a heteroaromatic ring with 5-30 ring atoms, Condensed rings with 8-30 ring atoms, C 1 -C 8 straight chain or branched alkanes, C 3 -C 10 alicyclic hydrocarbons, C 1 -C 8 alkoxy groups, the substituents can be C 6 -C 30 aromatic rings, C 5 -C 30 heteroaromatic rings, C 10 -C 30 fused rings, C 1 -C 8 straight chain or branched alkanes, C 3 -C 10 alicyclic hydrocarbons, C 1 -C 8 alkoxy groups , allyl, cyano, halogen, hydrogen or deuterium, two adjacent R 4 can be fused with each other to form a ring;

The definition of Y is the same as claim 1.
The organic compound according to any one of claims 1 to 3, wherein when R 1 -R 4 occur multiple times, they can be identically or differently selected from one of the following structural groups or a combination thereof:

in:

When V occurs multiple times, the same or different ones are independently selected from CR 6 or N;

When Q appears multiple times, it can be independently selected from BR 7 , C(=O), C(R 7 R 8 ), NR 9 , O, S, P, P=O or P=S;

The definitions of R 6 -R 9 are the same as the definition of R 1 in claim 1.
The organic compound according to any one of claims 1 to 3, wherein when R 1 -R 3 appear multiple times, they may be identical or different selected from or substituted by an electron-withdrawing group.
The organic compound according to claim 5, wherein the electron-withdrawing group is selected from one or more of F, cyano or the following groups:

in:

n is 1, 2 or 3;

R 11 can be a substituted or unsubstituted C 6 -C 30 aromatic ring, a heteroaromatic ring with 5-30 ring atoms, a condensed ring with 8-30 ring atoms, C 1 -C 8 straight chain or branched chain Alkanes, C 3 -C 10 alicyclic hydrocarbons, C 1 -C 8 alkoxy groups, where the substituents can be C 6 -C 30 aromatic rings, C 5 -C 30 heteroaromatic rings, C 10 -C 30 fused rings, C 1 -C 8 straight chain or branched alkanes, C 3 -C 10 alicyclic hydrocarbons, C 1 -C 8 alkoxy groups, allyl groups, cyano groups, halogens, hydrogen or deuterium;

W is selected from CR 101 or N, and at least one is N, and any two adjacent positions can form a monocyclic or polycyclic aliphatic or aromatic ring system;

M 1 , M 2 and M 3 independently represent C(R 102 R 103 ), NR 103 , Si(R 103 R 104 ), O, C=N(R 105 ), C=C(R 105 R 106 ) or none;

The definitions of R 101 -R 106 are the same as the definition of R 1 in claim 1.
A high polymer comprises at least one repeating unit, and the repeating unit comprises a structural unit represented by general formula (I).
A mixture comprising an organic compound as claimed in any one of claims 1 to 6 or a polymer as claimed in claim 7, and at least one organic functional material, which can be selected from empty Hole injection material, hole transport material, electron transport material, electron injection material, electron blocking material, hole blocking material, phosphor host material.
The mixture according to claim 8, wherein the organic functional material is selected from compounds represented by the following general formula (IV):

in:

A is selected from substituted or unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups with 5-100 ring atoms;

D is an electron-rich group;

p is any integer of 1-6.
A composition comprising an organic compound as claimed in any one of claims 1 to 6 or a polymer as claimed in claim 7 or a mixture as claimed in claim 8 or 9, and at least one organic solvent.
An organic electronic device comprising a functional layer comprising at least one organic compound as claimed in any one of claims 1 to 6 or the polymer as claimed in claim 7 or claim 8 or 9 the mixture described.
The organic electronic device according to claim 11, characterized in that, the organic electronic device is an electroluminescent device, and comprises a light-emitting layer, and the light-emitting layer comprises a light-emitting layer as described in any one of claims 1 to 6 The organic compound or the high polymer as claimed in claim 7 or the mixture as claimed in claim 8 or 9.