Organic heterocyclic compounds and use in organic light emitting diodes

Abstract

Provided are an organic heterocyclic compound and applications thereof in organic light-emitting diodes. The organic compound has good carrier balance and fluorescence quantum efficiency, realizes high efficiency and long service life of an OLED device, and thus has great application potential and application range. Also provided are a mixture, a composition and an organic electronic device comprising the organic compound.

Description

Technical Field

[0001] The present invention relates to the field of electroluminescent materials, and in particular to an organic heterocyclic compound, a mixture or composition containing the same, and its use in organic electronic devices, especially in organic electroluminescent devices. The present invention also relates to an organic electronic device containing the organic compound according to the present invention, and its use. Background Art

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

[0003] Organic electroluminescence (OLED) refers to the conversion of electrical energy into light energy using organic substances. OLED elements that utilize this phenomenon typically have a positive electrode and a negative electrode with an organic layer between them. To improve the efficiency and lifespan of OLED elements, the organic layer has a multilayer structure, with each layer containing 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 such an OLED element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, and electrons are injected from the negative electrode into the organic layer. When the injected holes and electrons meet, excitons are formed, which then emit light when they transition back to the ground state. Such OLED elements exhibit characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

[0004] Both theory and experiment have proven that the luminescent material is the most important factor in determining the efficiency of OLED devices. Currently, the luminescent layer of organic electroluminescent elements typically uses a mixed system of host / guest materials as the luminescent material, which can improve color purity, luminous efficiency, and stability. Generally speaking, when using a host / guest material system, the selection of the host material is crucial because the host material greatly affects the efficiency and stability of the OLED device. Preferably, the host material should have an appropriate 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 formation of amorphous thin films, good interfacial interaction with adjacent functional layer materials, and low molecular motion.

[0005] Especially for phosphorescent red light hosts, the material must have good carrier transport capabilities and a suitable triplet energy level to ensure that energy can be effectively transferred to the guest material during the luminescence process, thereby achieving high efficiency. Currently reported red light hosts are generally large conjugated aromatic rings, such as the fused-ring carbazole derivatives reported in WO2012169821, WO2012165844, and WO2016013817. These reported compounds suffer from low device efficiency and poor stability, and also ignore the balance of carrier transport in the host material within the device.

[0006] Therefore, further development of red phosphorescent host materials is needed to improve the efficiency and lifespan of OLED devices. Summary of the Invention

[0007] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide an organic compound, including a mixture, a composition, an organic electronic device and applications thereof, in order to solve the problems of efficiency and life span of existing OLEDs.

[0008] The technical solutions of the present invention are as follows:

[0009] An organic compound comprising a structure as shown in general formula (I):

[0010]

[0011] 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 C6-C 30 an aromatic ring, a heteroaromatic ring having 5-30 ring atoms, or a fused ring structural unit having 8-30 ring atoms, wherein the G ring may be absent;

[0012] X are the same or different and are independently selected from C or N;

[0013] Y is selected from BR1, C(R1R2), NR3, Si(R1R2), O or S, and R1-R3, at each occurrence, are independently selected from H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; and when R1-R3 are substituted, the adjacent two carbon atoms in the same aromatic ring in the substituent may be fused to form a ring.

[0014] A polymer comprises at least one repeating unit, wherein the repeating unit comprises a structural unit represented by general formula (I).

[0015] A mixture comprising an organic compound or polymer as described above, and at least one organic functional material, wherein the organic functional material can be selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores or host materials.

[0016] A composition comprises an organic compound or polymer or mixture as described above, and at least one organic solvent.

[0017] An organic electronic device comprises at least one organic compound, polymer or mixture as described above.

[0018] Beneficial Effects: The organic compounds of the present invention utilize a large conjugated aromatic system to connect nitrogen-based electron-withdrawing structural units. Combined with suitable p-type materials, they can further improve carrier transport balance, significantly increasing device efficiency and extending device life. The organic compounds of the present invention can be used as light-emitting layer materials. By combining them with other suitable materials, they can enhance the luminous efficiency and lifespan of electroluminescent devices, providing a solution for low-cost, high-efficiency, and long-life light-emitting devices. DETAILED DESCRIPTION

[0019] The present invention provides an organic compound and its application in an organic electroluminescent device. To make the objectives, technical solutions, and effects of the present invention more clear and explicit, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0020] In the present invention, composition and printing ink, or ink have the same meaning and can be used interchangeably.

[0021] In the present invention, main material, matrix material, host or matrix material have the same meaning and can be interchanged.

[0022] In the present invention, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0023] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a carbazolyl group is 12.

[0024] In the embodiments of the present invention, the energy level structure of the organic material, the singlet energy level S1, the triplet energy level T1, the HOMO, and the LUMO play a key role. The following is an introduction to the determination of these energy levels.

[0025] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0026] The triplet energy level T1 of an organic material can be measured by low-temperature time-resolved luminescence spectroscopy; T1 and S1 can also be obtained by quantum simulation calculations (e.g., by time-dependent DFT), such as using the commercial software Gaussian 09W (Gaussian Inc.). Specific simulation methods can be found in WO2011141110 or described in the Examples below. ΔE ST Defined as (S1-T1).

[0027] It should be noted that the absolute values ​​of HOMO, LUMO, S1, and 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, may give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values ​​of HOMO, LUMO, S1, and T1 are based on Time-dependent DFT simulations, 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).

[0028] In the present invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on.

[0029] The present invention provides an organic compound represented by the general formula (I):

[0030]

[0031] 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 C6-C 30 an aromatic ring, a heteroaromatic ring having 5 to 30 ring atoms, or a fused ring structural unit having 8 to 30 ring atoms; the G ring may be absent; the Xs are identical or different and are independently selected from C or N; Y is selected from BR1, C(R1R2), NR3, Si(R1R2), O or S, and each occurrence of R1-R3 is independently selected from H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or a keto group having 2 to 20 C atoms C atoms, or an alkoxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; and when R1-R3 are substituted, the adjacent two carbon atoms in the same aromatic ring in the substituents of R1-R3 may be fused into a ring.

[0032] An 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 having two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., a fused ring. A fused heterocyclic aromatic group refers to a fused heterocyclic aromatic hydrocarbon group containing at least one heteroatom. For the purposes of this invention, aromatic or heterocyclic aromatic groups include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, and carbene are also considered aromatic or heterocyclic aromatic groups for this purpose. For the purposes of this invention, fused ring aromatic or heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which multiple aromatic or heterocyclic aromatic groups are interrupted by short non-aromatic units (<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, triarylamines, diaryl ethers, etc. are also considered fused aromatic ring systems for the purposes of this invention.

[0033] Specific examples of the fused ring aromatic group include naphthalene, anthracene, fluoranthene, phenanthrene, phenalene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

[0034] Specific examples of fused heterocyclic aromatic groups include benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0035] A linear alkane group refers to an alkane in which the carbon atoms are connected by a single, straight chain. When the number of carbon atoms exceeds three, the alkane chain can form branched structures in addition to straight chains. These are branched alkanes. When the number of carbon atoms exceeds three, in addition to forming straight or branched chains, the carbon atoms can also form cyclic alkanes by single or double bonds. These are alicyclic hydrocarbons. Alicyclic hydrocarbons can also contain two or more carbon rings, which can be connected in a variety of ways: two rings in a molecule can share a single carbon atom, a system called a spirocycle; two carbon atoms in a ring can be connected by a carbon bridge, forming a bicyclic or polycyclic ring system, called a bridged ring; and several rings can also be connected to form a cage-like structure.

[0036] Specific examples of the C1-C8 straight-chain alkane group include: methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0037] Specific examples of C1-C8 branched alkane groups include isopropyl, tert-butyl, isopentane, neopentane, dimethylhexane, trimethylpropane, 2,3-dimethylbutane, 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, 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 derivatives thereof.

[0038] Specific examples of C3-C8 alicyclic hydrocarbon groups include: 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.

[0039] Alkoxy refers to an alkyl group combined with an oxygen atom. Depending on the type of alkyl group, it can be further divided into those connected by a branched or branched alkyl group and oxygen, such as methoxy, ethoxy, propoxy, tert-butoxy, etc., and those connected by a cycloalkane and oxygen, such as cyclopropyloxy, cyclohexyloxy, etc.

[0040] Specifically, examples of C1-C8alkoxy groups include methoxy, ethoxy, propoxy, 2-methylethoxy, cyclopropyloxy, n-butyloxy, t-butyloxy, cyclobutyloxy, 2-methylpropyloxy, 3-methylpropyloxy, n-pentyloxy, cyclopentyloxy, isopentyloxy, neopentyloxy, dimethylhexyloxy, trimethylpropyloxy, 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, n-heptyloxy, cycloheptyloxy, 2-methylheptyloxy, 3-methylheptyloxy, 4-methylheptyloxy, n-octyloxy, cyclooctyloxy, 3-ethylhexyloxy, 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 derivatives thereof.

[0041] In certain preferred embodiments, the A, B, C, D, E, F and G rings of the organic compound are the same or different and are independently selected from the group consisting of substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, fluoranthene, pyrene, fluorene, pyrrole, furan, thiophene, pyridine, cyclopentadiene, dibenzofuran and the like, wherein at least one of the A, B, C, D and E rings is a five-membered ring, and two adjacent rings can be fused, and the G ring represents a ring that can be fused to the B ring.

[0042] In certain embodiments, the G ring is null.

[0043] In certain more preferred embodiments, the A, B, C, D and E rings can be further selected from one or more combinations comprising the following structural groups, wherein the H on the ring can be optionally substituted:

[0044]

[0045] In some preferred embodiments, the organic compound has a structure according to Formula (II-a) or (II-b):

[0046]

[0047] wherein: X1-X 16 are the same or different and are independently selected from CR4or N, wherein R4may be a substituted or unsubstituted C6-C 30 aromatic ring, heteroaromatic ring having 5-30 ring atoms, fused ring having 8-30 ring atoms, C1-C8straight or branched chain alkane, C3-C8cycloalkane, C1-C8alkoxy, wherein the substituents can be C6-C 10 alicyclic hydrocarbon, C1-C8alkoxy, wherein the substituents can be C6-C 30Aromatic ring, C5-C 30 Heteroaromatic ring, C 10 -C 30 Condensed ring, C1-C8 straight chain or branched chain alkane, C3-C 10 Alicyclic hydrocarbon, C1-C8 alkoxy, allyl, cyano, halogen, hydrogen or deuterium, two adjacent R4 can be fused to form a ring; Y is as defined above.

[0048] In some preferred embodiments, the core structure of the organic compound, that is, the general formula (I) or (II-a) or (II-b) excluding all substituents, is a condensed ring compound with no more than 45 ring atoms, preferably a condensed ring compound with no more than 40 ring atoms, more preferably a condensed ring compound with no more than 35 ring atoms, and most preferably a condensed ring structure with no more than 30 ring atoms.

[0049] In some more preferred embodiments, the structure of the organic compound is as shown in formula (III-a) or (III-b):

[0050]

[0051] Wherein: R5 is defined the same as R4 above, and Y is defined the same as above.

[0052] In some preferred embodiments, when the above R1-R5 appear multiple times, they may be the same or different and selected from one or a combination of the following structural groups:

[0053]

[0054] Wherein: V, when it occurs multiple times, is the same or different and is independently selected from CR6 or N; Q, when it occurs multiple times, can be independently selected from BR7, C(=O), C-(R7R8), NR9, O, S, P, P=O or P=S, wherein R6-R9 are defined the same as R1 above.

[0055] In some more preferred embodiments, the R1-R5 can be further selected from one or more combinations of the following structural groups, wherein the H on the ring can be arbitrarily substituted:

[0056]

[0057]

[0058] Where n1 is 1 or 2 or 3 or 4.

[0059] In some preferred embodiments, the substituents in the organic compound, such as R1-R5, can be connected to the aromatic ring via a L group, wherein L is selected from the group consisting of one or more of the following structures, wherein the H on the ring can be optionally substituted:

[0060]

[0061] In some most preferred embodiments, the organic compound described above, wherein the L group can comprise a structure according to the following formula, wherein the H on the ring can be optionally substituted:

[0062]

[0063] In some preferred embodiments, the organic compound described above, the substituents R1-R3 connected to Y can be an electron withdrawing group or substituted with an electron withdrawing group. Suitable electron withdrawing groups can be selected from F, cyano, or one or more of the following groups in combination:

[0064]

[0065] wherein: n is 1, 2, or 3; W is selected from CR 101 or N, and at least one is N, while any two adjacent positions can form a monocyclic or polycyclic aliphatic or aromatic ring system; M 1 , M 2 and M 3 are each independently C(R 102 R 103 ), NR 103 , Si(R 103 R 104 ), O, C=N(R 105 ), C=C(R 105 R 106 ), or null; R 11 may be a substituted or unsubstituted C6-C 30 aromatic ring, a heteroaromatic ring having 5-30 ring atoms, a fused ring having 8-30 ring atoms, a C1-C8 straight chain or branched alkyl, a C3-C 10 alicyclic hydrocarbon, a C1-C8 alkoxy, wherein the substituents of R 11 may be a C6-C 30 aromatic ring, a C5-C 30 heteroaromatic ring, a C 10 -C 30 fused ring, a C1-C8 straight chain or branched alkyl, a C3-C 10 alicyclic hydrocarbon, a C1-C8 alkoxy, an allyl group, a cyano group, a halogen, hydrogen, or deuterium; R 101 -R 106 is defined the same as R1.

[0066] In other preferred embodiments, in the above organic compound, the electron-withdrawing group is selected from one or more combinations of the following groups:

[0067]

[0068] In certain preferred embodiments, the organic compounds according to the present invention have a small singlet-triplet energy level difference, typically ΔE st ≤0.3eV, preferably ΔE st ≤0.2eV, preferably ΔE st ≤0.15eV, preferably ΔE st ≤0.10eV.

[0069] Depending on the substitution pattern, organic compounds according to the general formulae (III-a)-(III-b) can have a variety of functions, including, but not limited to, hole transport, electron transport, luminescence, and exciton blocking. In particular, the substituents R1-R5 describe which compounds are particularly suitable for which functions. The substituents R1-R5 influence the electronic properties of the units of the general formulae (III-a)-(III-b).

[0070] In a more preferred embodiment, the organic compound according to the present invention is at least partially H-deuterated, preferably 10% H-deuterated, more preferably 20% H-deuterated, most preferably 30% H-deuterated, and most preferably 40% H-deuterated.

[0071] The specific structures of the organic compounds according to the present invention are listed below, but are not limited thereto. These structures can be substituted at all possible substitution sites.

[0072]

[0073]

[0074]

[0075]

[0076]

[0077] The organic compounds of the present invention can be used as functional materials in electronic devices, particularly OLED devices. Organic functional materials can be divided into hole injection materials (HIMs), hole transport materials (HTMs), electron transport materials (ETMs), electron injection materials (EIMs), electron blocking materials (EBMs), hole blocking materials (HBMs), emitters, host materials, and organic dyes.

[0078] In a preferred embodiment, the organic compound according to the present invention can serve as a host material or an electron transport material or a hole transport material.

[0079] In a preferred embodiment, the organic compounds according to the present invention can serve as phosphorescent host materials or co-host materials.

[0080] Phosphorescent host materials must have an appropriate triplet energy level, i.e., T1. In certain embodiments, the organic compounds according to the present invention have T1 ≥ 2.2 eV, preferably ≥ 2.4 eV, more preferably ≥ 2.6 eV, even more preferably ≥ 2.65 eV, and most preferably ≥ 2.7 eV.

[0081] Organic functional materials preferably have good thermal stability. Generally, the organic compounds according to the present invention have a glass transition temperature (Tg) of 100°C or higher. In a preferred embodiment, Tg is 120°C or higher. In a more preferred embodiment, Tg is 140°C or higher. In an even more preferred embodiment, Tg is 160°C or higher. In a most preferred embodiment, Tg is 180°C or higher.

[0082] In certain preferred embodiments, the organic compounds according to the present invention have ((HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, and most preferably ≥ 0.45 eV.

[0083] In other preferred embodiments, the organic compound according to the present invention has ((LUMO+1)-LUMO) ≥ 0.15 eV, preferably ≥ 0.20 eV, more preferably ≥ 0.25 eV, even more preferably ≥ 0.30 eV, and most preferably ≥ 0.35 eV.

[0084] In some embodiments, the organic compound according to the present invention has a luminescent function, and the luminescent wavelength is between 300-1000 nm, preferably between 350-900 nm, and more preferably between 400-800 nm. The luminescence referred to here refers to photoluminescence or electroluminescence.

[0085] The present invention also relates to a polymer, wherein at least one repeating unit comprises a structure as shown in general formula (I).

[0086] In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit represented by general formula (I) is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

[0087] As defined herein, the term "small molecule" refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, a small molecule lacks a repeating structure. A small molecule has a molecular weight of ≤4000 g / mol, preferably ≤3000 g / mol, and most preferably ≤2000 g / mol.

[0088] Polymers include homopolymers, copolymers, and block copolymers. In the present invention, polymers also include dendrimers. For information on the synthesis and application of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

[0089] Conjugated polymer is a polymer whose main chain backbone is mainly composed of sp 2 Hybrid orbitals are formed. Famous examples include polyacetylene and poly(phenylenevinylene). The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp 2 When hybridization is interrupted by some natural defects, it is still considered a conjugated polymer. In addition, the conjugated polymers in the present invention also include those containing aryl amines, aryl phosphine, other heteroaromatics, organometallic complexes, etc. in the main chain.

[0090] In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0091] 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, even more preferably ≥ 160°C, and most preferably ≥ 180°C.

[0092] In a preferred embodiment, the molecular weight distribution (PDI) of the polymer according to the present invention is preferably in the range of 1 to 5, more preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1 to 1.5.

[0093] In a preferred embodiment, the polymer according to the present invention has a weight average molecular weight (Mw) preferably in the range of 10,000 to 1,000,000, more preferably 50,000 to 500,000, more preferably 100,000 to 400,000, even more preferably 150,000 to 300,000, and most preferably 200,000 to 250,000.

[0094] The present invention also relates to a mixture comprising one of the above-mentioned organic compounds or polymers (H1) and at least another organic functional material (H2). The organic functional material includes a hole (also known as an electron hole) injection or transport material (HIM / HTM), a hole blocking material (HBM), an electron injection or transport material (EIM / ETM), an electron blocking material (EBM), an organic host material (Host), a singlet light emitter (fluorescent light emitter), a triplet light emitter (phosphorescent light emitter), an organic thermally excited delayed fluorescence material (TADF material), and in particular a luminescent organometallic complex. 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 by reference. The organic functional material can be a small molecule or a polymer material.

[0095] In a preferred embodiment, the mixture comprises at least one organic compound or polymer according to the present invention and a phosphorescent emitter. The organic compound or polymer according to the present invention can serve as a phosphorescent host material, wherein the phosphorescent emitter is present in an amount of ≤20 wt %, preferably ≤15 wt %, and more preferably ≤10 wt %.

[0096] In another preferred embodiment, the 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 this embodiment, the organic compound or polymer according to the present invention can serve as an auxiliary luminescent material, with the weight ratio of the organic compound or polymer to the phosphorescent emitter ranging from 1:2 to 2:1. In another preferred embodiment, the organic compound or polymer according to the present invention forms an exciplex with the other host material, wherein the exciplex has a higher energy level than the phosphorescent emitter.

[0097] In another preferred embodiment, the mixture comprises at least one organic compound or polymer according to the present application and one TADF material. Here the organic compound or polymer according to the present application can act as host material for the TADF light emitter, wherein the weight percentage of the TADF material is < 15 wt.-%, preferably < 10 wt.-%, more preferably < 8 wt.-%.

[0098] In another preferred embodiment, the mixture comprises at least one organic compound or polymer according to the present application and one HTM material.

[0099] In a very preferred embodiment, the mixture comprises at least one organic compound or polymer according to the present application and another host material (singlet or triplet host material). Here the organic compound or polymer according to the present application can act as second host material, wherein the weight percentage is in the range of 30 to 70 %, preferably 40 to 60 %.

[0100] For further details regarding host materials, phosphorescent emitter materials, HTM, fluorescent emitter materials and TADF materials, reference is made to WO 2018095395, the entire content of which is hereby incorporated by reference.

[0101] In a particularly preferred embodiment, the mixture comprises at least one organic compound or polymer according to the present application (H1) and another organic functional material (H2). Such a mixture can act as a phosphorescent hybrid host material and can further comprise a phosphorescent emitter, wherein the weight percentage of the phosphorescent emitter is < 20 wt.-%, preferably < 15 wt.-%, more preferably < 10 wt.-%.

[0102] In the following, the mixture comprising at least one organic compound or polymer according to the present application (H1) and another organic functional material (H2) as phosphorescent hybrid host material is described in more detail.

[0103] In a preferred embodiment, the other organic functional material (H2) has hole-transporting properties.

[0104] More preferably, the other organic functional material (H2) has both hole-transporting and electron-transporting properties.

[0105] Generally, the molar ratio of the organic compound or polymer according to the present application (H1) to the other organic functional material (H2) is in the range of 1 :9 to 9:1.

[0106] Preferably, the molar ratio of the organic compound or polymer according to the present application (H1) to the other organic functional material (H2) is in the range of 3:7 to 7:3.

[0107] More preferably, the molar ratio of the organic compound or polymer (H1) of the present invention to the other organic functional material (H2) is in the range of 4:6 to 6:4.

[0108] Optimally, the molar ratio of the organic compound or polymer (H1) of the present invention to the other organic functional material (H2) is 5:5.

[0109] In a preferred embodiment, in the mixture, the other organic functional material (H2) is selected from the compounds represented by the following general formula (IV):

[0110]

[0111] Wherein: A is selected from a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 100 ring atoms; D is an electron-rich group; and p is any integer from 1 to 6.

[0112] In certain preferred embodiments, the electron-rich (or electron-donating) group D in formula (IV) comprises any of the following groups:

[0113]

[0114] in:

[0115] Ar1 represents an aromatic group or heteroaromatic group having 5 to 40 ring atoms;

[0116] Z 1 , Z 2 , Z 3 Each independently represents a single bond, C-(R 201 )2、NR 202 、Si-(R 203 )2, O, C(=O), S or S=O, but Z 2 and Z 3 Not all are single bonds;

[0117] R 4 and R 5 The definitions of R4 and R 201 -R 203 The definition is the same as that of R1 above.

[0118] In some more preferred embodiments, the electron-rich (or electron-donating) group D in the general formula (IV) comprises any of the following groups:

[0119]

[0120] where R 4 The definition of is the same as above.

[0121] In certain preferred embodiments, p is 1 or 2 or 3 or 4; in more preferred embodiments, p is 1 or 2 or 3; in most preferred embodiments, p is 1 or 2.

[0122] In some preferred embodiments, the mixture according to the present application, the other organic functional material (H2) is selected from one of the following structural formulae:

[0123]

[0124] wherein A is as defined above and Ar2 has the same meaning as Ar1.

[0125] In certain embodiments, the mixture according to the present application, H1 or H2 has a high triplet energy level T1, typically T1≥ 2.2 eV, more preferably T1≥ 2.3 eV, even more preferably T1≥ 2.4 eV, even more preferably T1≥ 2.5 eV, most preferably T1≥ 2.6 eV.

[0126] In certain preferred embodiments, the organic mixture, H1 and H2 form a type II heterojunction structure, i.e. the highest occupied molecular orbital (HOMO) of H1 is lower than the HOMO of H2 and the lowest unoccupied molecular orbital (LUMO) of H1 is lower than the LUMO of H2.

[0127] In a more preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤ min(T1(H1), T1(H2))+0.1 eV, wherein LUMO(H1), HOMO(H1) and T1(H1) are the lowest unoccupied molecular orbital, the highest occupied molecular orbital and the triplet energy level of H1, respectively, and LUMO(H2), HOMO(H2) and T1(H2) are the lowest unoccupied molecular orbital, the highest occupied molecular orbital and the triplet energy level of H2, respectively.

[0128] In a preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤ min(T1(H1), T1(H2));

[0129] In a more preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤ min(T1(H1), T1(H2))-0.05 eV;

[0130] In a more preferred embodiment, the mixture min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) < min(T1(H1), T1(H2)) - 0.1 eV;

[0131] In a very preferred embodiment, the mixture min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) < min(T1(H1), T1(H2)) - 0.15 eV;

[0132] In a most preferred embodiment, the mixture min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) < min(T1(H1), T1(H2)) - 0.2 eV.

[0133] In the following, further examples of organic functional materials (H2) according to general formula (IV) are given, without being limited thereto:

[0134]

[0135]

[0136] In a preferred embodiment, the mixture according to the present application, wherein at least one of H1 and H2, preferably H1, has ((LUMO+1)-LUMO) > 0.1 eV, preferably > 0.15 eV, more preferably > 0.20 eV, even more preferably > 0.25 eV, most preferably > 0.30 eV.

[0137] In another preferred embodiment, the mixture according to the present application, wherein at least one of H1 and H2, preferably H2, has (HOMO-(HOMO-1)) > 0.2 eV, preferably > 0.25 eV, more preferably > 0.30 eV, even more preferably > 0.35 eV, most preferably > 0.40 eV.

[0138] It is an object of the present application to provide material solutions for evaporation-type OLEDs.

[0139] In a preferred embodiment, the mixture according to the present application is used in an evaporation-type OLED device. For this purpose, H1 and H2 in the organic compounds or mixtures according to the present application have a molecular weight < 1000 g / mol, preferably < 900 g / mol, very preferably < 850 g / mol, more preferably < 800 g / mol, most preferably < 700 g / mol.

[0140] In a preferred embodiment, in the mixture, the difference in molecular weight between H1 and H2 does not exceed 100 Dalton; preferably, the difference in molecular weight does not exceed 60 Dalton; more preferably, the difference in molecular weight does not exceed 30 Dalton.

[0141] In another preferred embodiment, in the mixture, the difference in sublimation temperature between H1 and H2 does not exceed 30K; preferably, the difference in sublimation temperature does not exceed 20K; more preferably, the difference in sublimation temperature does not exceed 10K.

[0142] Another object of the present invention is to provide a material solution for printed OLEDs.

[0143] 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 and most preferably ≥1100 g / mol.

[0144] In vapor-deposited OLEDs, the two host materials in a premixed co-host 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 film formation and, therefore, device performance. In addition to molecular weight and sublimation temperature, these properties may also include other properties, such as glass transition temperature and different molecular volumes. Preferred embodiments of the mixture for printed OLEDs according to the present invention include one or a combination of two or more of the following:

[0145] 1) The difference in molecular weight between H1 and H2 is ≥120 g / mol, preferably ≥140 g / mol, more preferably ≥160 g / mol, and most preferably ≥180 g / mol.

[0146] 2) The difference in sublimation temperature between H1 and H2 is ≥60K, preferably ≥70K, more preferably ≥75K, and most preferably ≥80K.

[0147] 3) The difference in glass transition temperature between H1 and H2 is ≥20K, preferably ≥30K, more preferably ≥40K, and most preferably ≥45K.

[0148] 4) The difference in molecular volume between H1 and H2 is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0149] In other embodiments, at least one, and preferably both, of H1 and H2 in the organic compound or mixture according to the present invention has a solubility in toluene of ≥2 mg / mL, preferably ≥3 mg / mL, more preferably ≥4 mg / mL, and most preferably ≥5 mg / mL at 25°C.

[0150] In a preferred embodiment, the mixture, wherein the molar ratio of H1 to H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; and the more preferred molar ratio is 4:6 to 6:4.

[0151] In other embodiments, the solubility of the organic compound according to the present invention in toluene at 25° C. is ≥10 mg / mL, preferably ≥15 mg / mL, and most preferably ≥20 mg / mL.

[0152] The present invention further relates to a composition or ink comprising an organic compound or polymer according to the present invention and at least one organic solvent.

[0153] When used in printing processes, ink viscosity and surface tension are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0154] In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm, more preferably in the range of 22 dyne / cm to 35 dyne / cm, and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0155] In another preferred embodiment, the viscosity of the ink according to the present invention is in the range of about 1 cps to 100 cps, preferably in the range of 1 cps to 50 cps, more preferably in the range of 1.5 cps to 20 cps, and most preferably in the range of 4.0 cps to 20 cps at the working temperature or 25° C. The composition thus formulated will facilitate inkjet printing.

[0156] Viscosity can be adjusted by various methods, such as by selecting the appropriate solvent and adjusting the concentration of the functional material in the ink. The ink containing the organic compound according to the present invention facilitates adjustment of the printing ink within 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 30% by weight, preferably in the range of 0.5% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, even more preferably in the range of 0.5% to 10% by weight, and most preferably in the range of 1% to 5% by weight.

[0157] 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, in particular aliphatic chain / ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0158] Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, 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, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 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-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4- Methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, 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-dimethoxytoluene, 4-ethylhexyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethylbenzene Oxybenzene, glycidyl phenyl 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, amyl ether, c-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; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

[0159] 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-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, amyl 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.

[0160] In some other embodiments, the printing ink further comprises another organic solvent. Examples of the other organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, 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, tetralin, decalin, indene, and / or mixtures thereof.

[0161] In a preferred embodiment, the composition according to the present invention is a solution.

[0162] In another preferred embodiment, the composition according to the present invention is a suspension.

[0163] 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 %, and most preferably 0.25 to 5 wt % of the organic compound or its mixture.

[0164] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0165] Suitable printing or coating techniques include, but are not limited to, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating or pad printing, slot extrusion coating, etc. Inkjet printing, nozzle printing, and gravure printing are preferred. The solution or suspension may further include one or more components such as a surfactant, lubricant, wetting agent, dispersant, hydrophobic agent, adhesive, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing techniques and their requirements for related solutions, such as solvents, concentrations, and viscosities, please refer to "Handbook of Print Media: Technologies and Production Methods," edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0166] Based on the above-mentioned organic compound, the present invention further provides an application of the above-mentioned organic compound or polymer, i.e., applying the organic compound or polymer to an organic electronic device. The organic electronic device may be selected from, but not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor (OLED), an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (OPED). Particularly preferred are organic electroluminescent devices, such as OLEDs, OLEECs, and organic light-emitting field-effect transistors. In an embodiment of the present invention, the organic compound is preferably used in the light-emitting layer of an electroluminescent device.

[0167] The present invention further relates to an organic electronic device comprising at least one of the organic compounds or polymers described above. Generally, such an organic electronic device comprises at least a cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one of the organic compounds or polymers described above. The organic electronic device may be selected from, but is 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 (OLEDs), organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes (OPDs). Particularly preferred are organic electroluminescent devices, such as OLEDs, OLEECs, and OLEDs.

[0168] In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer, which comprises one of the organic compounds or polymers, or comprises one of the organic compounds or polymers and a phosphorescent light-emitting body, or comprises one of the organic compounds or polymers and a host material, or comprises one of the organic compounds or polymers, a phosphorescent light-emitting body and a host material.

[0169] The electroluminescent device described above, especially the OLED, includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0170] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting element. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best if the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from a polymer film or plastic with a glass transition temperature Tg of above 150°C, preferably above 200°C, more preferably above 250°C, and most preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene (2,6-naphthalene) (PEN).

[0171] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can readily inject holes into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In a preferred embodiment, the absolute difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting material 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), 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 patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0172] The cathode can comprise a conductive metal or metal oxide. The cathode can readily inject electrons into the EIL or ETL or directly into the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the light emitter in the light-emitting layer or of the n-type semiconductor material as electron injection layer (EIL) or 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 that can be used as cathode for an OLED can be used as cathode material for the inventive device. 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, and the like. 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, e-beam, and the like.

[0173] The OLED can also comprise other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL). Suitable materials 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 by reference.

[0174] In a preferred embodiment, the light-emitting layer in the light-emitting device according to the present application is prepared from a composition according to the present application.

[0175] The light-emitting device according to the present application has an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0176] The present application also relates to the use of an organic electronic device according to the present application in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0177] The present application also relates to electronic devices comprising an organic electronic device according to the present application, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0178] The present invention will be described below 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 concept of the present invention, those skilled in the art should realize 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.

[0179] Example 1

[0180]

[0181] Under nitrogen, a 2000 mL, dry, clean three-necked flask was charged with 1-bromocarbazole (100 g, 632 mmol), o-nitrophenylboronic acid (105.5 g, 632 mmol), tetrakis(triphenylphosphine)palladium (36.5 g, 31.6 mmol), and cesium carbonate (205.9 g, 632 mmol). 1000 mL of a tetrahydrofuran / water mixture (THF:H2O = 10:1) was added. The mixture was evacuated and filled with nitrogen five times, then heated to 110°C and stirred for 12 h. After the reaction was complete, the solvent was removed by rotary evaporation. The organic phases were extracted three times with dichloromethane and saturated brine. The combined organic phases were dried, filtered, and isolated by silica gel column chromatography (dichloromethane:petroleum ether = 5:1) to afford intermediate 1a (23 g, 83% yield).

[0182] Under nitrogen, intermediate 1a (80 g, 277 mmol), 1,8-dibromonaphthalene (79.3 g, 277 mmol), sodium tert-butoxide (31.9 g, 332.4 mmol), and tri-tert-butylphosphine (67.3 g, 332.4 mmol) were placed in a 1000 mL, dry, clean three-necked flask. 500 mL of dry toluene was added and the mixture was evacuated and filled with nitrogen five times. The mixture was then heated to 110°C and stirred for 12 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The mixture was extracted three times with dichloromethane and saturated brine. The organic phases were combined, dried, filtered, and isolated by silica gel column chromatography (dichloromethane:petroleum ether = 5:1) to afford intermediate 1b (23 g, 83% yield).

[0183] Under nitrogen, a clean, dry 500-mL three-necked flask was charged with intermediate 1b (30 g, 60.8 mmol), cesium carbonate (19.8 g, 60.8 mmol), bis(tricyclohexylphosphine)palladium dichloride (11.9 g, 15.2 mmol), and pivalic acid (70 mL, 60.8 mmol). 200 mL of dry toluene was added and the mixture was evacuated and filled with nitrogen five times. The mixture was then heated to 110°C and stirred for 12 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The mixture was extracted three times with dichloromethane and saturated brine. The organic phases were combined, dried, filtered, and isolated by silica gel column chromatography (dichloromethane:petroleum ether = 5:1) to afford intermediate 1c (23 g, 83% yield).

[0184] Under a nitrogen atmosphere, intermediate 1c (18 g, 43.6 mmol) and triethoxyphosphine (5.8 g, 43.6 mmol) were added to a clean, dry 500 mL three-necked flask. After five cycles of vacuum and nitrogen refilling, the mixture was heated to 110°C and stirred for 12 hours. After completion of the reaction, the solvent was removed by rotary evaporation. The mixture was extracted three times with dichloromethane and saturated brine. The organic phases were combined, dried, filtered, and isolated by silica gel column chromatography (dichloromethane:petroleum ether = 5:1) to afford intermediate 1d (23 g, 83% yield).

[0185] Under nitrogen atmosphere, intermediate 1d (8.7 g, 22.8 mmol), compound 1e (8.2 g, 22.8 mmol), trisdibenzylideneacetone dipalladium (1.04 g, 1.14 mmol), and sodium tert-butoxide (2.63 g, 27.4 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (4.6 g, 22.8 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:20) to obtain 7.79 g of solid powder with a yield of 58.6%.

[0186] Example 2

[0187]

[0188] Under nitrogen atmosphere, intermediate 1d (8.7 g, 22.8 mmol), compound 2a (8.2 g, 22.7 mmol), trisdibenzylideneacetone dipalladium (1.04 g, 1.14 mmol), and sodium tert-butoxide (2.63 g, 27.4 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (4.6 g, 22.8 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:20) to obtain 8.24 g of solid powder with a yield of 62%.

[0189] Example 3

[0190]

[0191] Under nitrogen atmosphere, intermediate 1d (12.4 g, 32.6 mmol), compound 3a (12.7 g, 32.6 mmol), trisdibenzylideneacetone dipalladium (1.5 g, 1.63 mmol), and sodium tert-butoxide (3.76 g, 39.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (6.6 g, 32.6 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:16) to obtain 11.06 g of solid powder with a yield of 55.2%.

[0192] Example 4

[0193]

[0194] Under nitrogen atmosphere, intermediate 1d (9.9 g, 26.1 mmol), compound 4a (8.5 g, 26.1 mmol), trisdibenzylideneacetone dipalladium (1.2 g, 1.3 mmol), and sodium tert-butoxide (2.5 g, 26.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (5.28 g, 26.1 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:10) to obtain 8.1 g of solid powder with a yield of 54.7%.

[0195] Example 5

[0196]

[0197] Under nitrogen atmosphere, intermediate 1d (9.9 g, 26.1 mmol), compound 5a (8.9 g, 26.1 mmol), trisdibenzylideneacetone dipalladium (1.2 g, 1.3 mmol), and sodium tert-butoxide (2.5 g, 26.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (5.28 g, 26.1 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:10) to obtain 9.3 g of solid powder with a yield of 62.9%.

[0198] Example 6

[0199]

[0200] Under nitrogen atmosphere, compound 6a (18.0 g, 51.9 mmol), compound 6b (8.9 g, 51.9 mmol), tetrakistriphenylphosphine palladium (0.6 g, 0.52 mmol) and X-Phos (0.6 g, 1.3 mmol) were added sequentially into a 500 mL three-necked flask. Then, 200 mL of toluene was injected into the flask and the flask was evacuated and replaced with nitrogen three times. Finally, 50 mL of an aqueous solution of potassium phosphate (13.2 g, 62.3 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 8 h. The solvent was removed by rotary evaporation and the mixture was extracted three times with dichloromethane and deionized water. The combined organic phases were separated and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 16.8 g of intermediate 6c with a yield of 72.6%.

[0201] Under nitrogen atmosphere, intermediate 1d (15.4 g, 40.6 mmol), intermediate 6c (16 g, 40.6 mmol), trisdibenzylideneacetone dipalladium (1.86 g, 2.03 mmol), and sodium tert-butoxide (4.68 g, 48.7 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (8.2 g, 40.6 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:20) to obtain 18.9 g of solid powder with a yield of 70.3%.

[0202] Example 7

[0203]

[0204] To a clean, dry 2000 mL three-necked flask, add 1-bromocarbazole (100 g, 457 mmol), 1-chloro-2-bromo-3-nitrobenzene (80 g, 457 mmol), tetrakistriphenylphosphine palladium (10 g), cesium carbonate (60 g), tetrahydrofuran, and water (1000 ml:200 ml). After five cycles of evacuation and nitrogen refilling, heat to 75°C and stir under reflux for 12 h. Cool to room temperature, pass through a silica gel column, spin dry, and separate by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid. Dry under vacuum at 60°C to yield 120.6 g of product 7a.

[0205] To a clean, dry, 1000-mL three-necked 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 evacuation and nitrogen refilling, heat to 100°C and reflux with stirring for 12 hours. Cool to room temperature, pass through a silica gel column, spin dry, extract with ethyl acetate and water, and separate by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid. Dry under vacuum at 60°C to yield 30.4 g of product 7b.

[0206] To a clean, dry 500 mL three-necked flask, add intermediate 7b (20 g, 46 mmol) and 40 g of triethylphosphine. After nitrogen replacement 4-5 times, heat to 100°C and stir for 24 hours. After concentration, extract three times with ethyl acetate and saturated sodium chloride solution. Column chromatography (ethyl acetate:petroleum ether 15:1) yields 12.3 g of 7c as a pale yellow solid.

[0207] To a clean, dry, 500-mL 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 evacuation and nitrogen refilling, heat to 100°C and reflux with stirring for 12 h. Cool to room temperature, pass through a silica gel column, spin dry, extract with ethyl acetate and water, and separate by column chromatography (ethyl acetate:petroleum ether 5:1) to obtain a pure white solid. Dry in vacuo at 60°C to yield 8.2 g of product 7d.

[0208] Under nitrogen atmosphere, intermediate 7d (8 g, 18 mmol), compound 1e (8.3 g, 18 mmol), trisdibenzylideneacetone dipalladium (1.04 g, 1.14 mmol) and sodium tert-butoxide (2.63 g, 27.4 mmol) were added sequentially to a 500 mL three-necked flask. 220 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (4.6 g, 22.8 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:20) to obtain 7.5 g of solid powder Comp-7 with a yield of 72.6%.

[0209] Example 8

[0210]

[0211] Under nitrogen atmosphere, intermediate 7d (9.6 g, 22.8 mmol), compound 2a (8.2 g, 22.7 mmol), trisdibenzylideneacetone dipalladium (1.04 g, 1.14 mmol), and sodium tert-butoxide (2.63 g, 27.4 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (4.6 g, 22.8 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:20) to obtain 8.24 g of solid powder with a yield of 62%.

[0212] Example 9

[0213]

[0214] Under nitrogen atmosphere, intermediate 7d (9.6 g, 32.6 mmol), compound 3a (12.7 g, 32.6 mmol), trisdibenzylideneacetone dipalladium (1.5 g, 1.63 mmol), and sodium tert-butoxide (3.76 g, 39.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (6.6 g, 32.6 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:16) to obtain 11.06 g of solid powder with a yield of 55.2%.

[0215] Example 10

[0216]

[0217] Under nitrogen atmosphere, intermediate 7d (10.9 g, 26.1 mmol), compound 4a (8.5 g, 26.1 mmol), trisdibenzylideneacetone dipalladium (1.2 g, 1.3 mmol), and sodium tert-butoxide (2.5 g, 26.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (5.28 g, 26.1 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:10) to obtain 8.1 g of solid powder with a yield of 54.7%.

[0218] Example 11

[0219]

[0220] Under nitrogen atmosphere, intermediate 7d (10.9 g, 26.1 mmol), compound 5a (8.9 g, 26.1 mmol), trisdibenzylideneacetone dipalladium (1.2 g, 1.3 mmol), and sodium tert-butoxide (2.5 g, 26.1 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (5.28 g, 26.1 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:10) to obtain 9.3 g of solid powder with a yield of 62.9%.

[0221] Example 12

[0222]

[0223] Under nitrogen atmosphere, compound 6a (18.0 g, 51.9 mmol), compound 6b (8.9 g, 51.9 mmol), tetrakistriphenylphosphine palladium (0.6 g, 0.52 mmol) and X-Phos (0.6 g, 1.3 mmol) were added sequentially into a 500 mL three-necked flask. Then, 200 mL of toluene was injected into the flask and the flask was evacuated and replaced with nitrogen three times. Finally, 50 mL of an aqueous solution of potassium phosphate (13.2 g, 62.3 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 8 h. The solvent was removed by rotary evaporation and the mixture was extracted three times with dichloromethane and deionized water. The combined organic phases were separated and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 16.8 g of intermediate 6c with a yield of 72.6%.

[0224] Under nitrogen atmosphere, intermediate 7d (17 g, 40.6 mmol), intermediate 6c (16 g, 40.6 mmol), trisdibenzylideneacetone dipalladium (1.86 g, 2.03 mmol) and sodium tert-butoxide (4.68 g, 48.7 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of dry toluene was then injected into the flask and the atmosphere was replaced with nitrogen three times under vacuum. Finally, tri-tert-butylphosphine (8.2 g, 40.6 mmol) was slowly added dropwise to the flask. The mixture was heated to 110°C and refluxed for 12 h. After completion of the reaction, the reaction mixture was poured into 500 mL of deionized water and stirred rapidly. During this period, the product precipitated continuously. After filtration, the product was dissolved again in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:20) to obtain 18.9 g of solid powder with a yield of 70.3%.

[0225] Example 13

[0226]

[0227] Under nitrogen atmosphere, compound 8a (20.2 g, 50 mmol), compound 8b (17.2 g, 100 mmol), tetrakis(triphenylphosphine)palladium (3.5 g, 3 mmol), tetrabutylammonium bromide (8.1 g, 25 mmol) and sodium hydroxide (4 g, 100 mmol) were added sequentially into a 500 mL three-necked flask, and then 200 mL of toluene and 50 mL of deionized water were added. The mixture was evacuated and replaced with nitrogen three times, and then heated at 110 °C with stirring for 24 h. After the reaction was terminated, most of the solvent was removed by rotary evaporation of the reaction solution, and the solution was dissolved in dichloromethane and washed three times with water. The combined organic phases were separated and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 18.7 g of intermediate 8c with a yield of 75%.

[0228] Intermediate 8c (14.9 g, 30 mmol) and 100 mL of N,N-dimethylformamide were added to a 250 mL single-necked flask. A 30 mmol solution of NBS in N,N-dimethylformamide was added dropwise under ice-cooling. The mixture was stirred in the dark for 12 h. After termination of the reaction, the reaction solution was poured into 300 mL of water and filtered. The residue was recrystallized to obtain 17.3 g of intermediate 8d in a 90% yield.

[0229] Under nitrogen atmosphere, intermediate 8d (34.4 g, 20 mmol), intermediate compound 8e (11.5 g, 20 mmol), tetrakis(triphenylphosphine)palladium (0.7 g, 0.6 mmol), tetrabutylammonium bromide (3.2 g, 10 mmol), and sodium hydroxide (1.6 g, 40 mmol) were added sequentially to a 500 mL three-necked flask. 200 mL of toluene and 50 mL of deionized water were then injected into the flask, and the flask was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and refluxed for 12 h. After completion of the reaction, the solvent was removed by rotary evaporation. The product was then dissolved in dichloromethane and extracted three times with saturated brine. The combined organic phases were separated and purified by silica gel column chromatography (eluent: dichloromethane:petroleum ether = 1:10) to obtain 18.7 g of solid powder with a yield of 85%.

[0230] Example 14

[0231]

[0232] Under nitrogen atmosphere, intermediate 8d (11.5 g, 20 mmol), compound 9a (44.4 g, 20 mmol), tetrakistriphenylphosphine palladium (0.7 g, 0.6 mmol), tetrabutylammonium bromide (3.2 g, 10 mmol), sodium hydroxide (1.6 g, 40 mmol), (10 mL) water and (80 mL) toluene were added to a 250 mL three-necked flask, heated at 110°C with stirring for 12 h, and the reaction was terminated. The reaction solution was rotary evaporated to remove most of the solvent, and the mixture was dissolved in dichloromethane and washed three times with water. 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%.

[0233] The energy levels of organic compound materials can be calculated through quantum calculations, such as using TD-DFT (time-dependent density functional theory) with Gaussian09W (Gaussian Inc.). For detailed simulation methods, see WO2011141110. The molecular geometry is first optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). The energy structure of the organic molecule is then calculated using TD-DFT (time-dependent density functional theory) using the "TD-SCF / DFT / Default Spin / B3PW91" basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated using the following calibration formulas, with S1, T1, and the resonance factor f(S1) used directly.

[0234] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0235] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0236] The 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:

[0237] Table 1

[0238]

[0239] Preparation and measurement of OLED devices

[0240] The following describes in detail the preparation process of the above-mentioned OLED device through a specific embodiment. The structure of the red OLED device is: ITO / HI / HI-1 / HT-2 / EML / ET: Liq / Liq / Al.

[0241]

[0242] The preparation steps are as follows:

[0243] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) to clean, and then perform UV ozone treatment;

[0244] b. HI (30 nm), HT-1 (60 nm), HT-2 (10 nm), main materials: 3% RD (40 nm), ET:Liq (50:50; 30 nm), Liq (1 nm), Al (100 nm) in high vacuum (1 × 10 -6 The ITO substrate was moved into a vacuum vapor deposition device and heated in a high vacuum (1×10 -6 mbar), a resistive heating evaporation source was used to form a 30nm thick HI layer, and a 60nm HT-1 and a 10nm HT-2 layer were sequentially heated on the HI layer. Comp-1 was then placed in one evaporation unit, and compound RD was placed in another evaporation unit as a guest. The materials were vaporized at different rates, so that the weight ratio of Comp-1:Dopant was 100:3, forming a 40nm light-emitting layer on the hole transport layer. ET and LiQ were then placed in different evaporation units and co-deposited at a ratio of 50% by weight, forming a 30nm electron transport layer on the light-emitting layer. Subsequently, 1nm of LiQ was deposited on the electron transport layer as an electron injection layer, and finally a 100nm thick Al cathode was deposited on the electron injection layer.

[0245] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0246] Device Examples 2-7 were implemented in the same manner as in Device Example 1, except that Comp-1 was replaced with Comp-2, Comp-4, and different co-hosts. Co-hosts refer to two compounds placed in different evaporation units to control the weight ratio of the materials.

[0247] The current-voltage-luminescence (IVL) characteristics of the red OLED devices were characterized using a characterization setup, recording key parameters such as efficiency, lifetime, and drive voltage. The performance of the red OLED devices is summarized in Table 2. The lifetime values ​​are relative to the comparative example.

[0248] Table 2

[0249]

[0250]

[0251] Testing showed that the luminous efficiency and lifetime of device examples 1 through 9 were significantly improved compared to those of comparative example 1. This indicates that the OLED devices fabricated using the organic compounds of this invention significantly enhance both luminous efficiency and lifetime. Device examples 10 through 17 employ the organic compounds of this invention in combination with other materials with hole-transporting capabilities to improve carrier balance, further enhancing the luminous efficiency and lifetime of the devices.

[0252] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. An organic compound having a structure represented by general formula (II-a) or (II-b): in: X1-X 16 are the same or different and are independently selected from CR4, wherein R4 are independently selected from substituted or unsubstituted C6-C 30 Aromatic ring, heteroaromatic ring with 5-30 ring atoms, C1-C8 straight or branched chain alkane, C3-C 10 Alicyclic hydrocarbon, C1-C8 alkoxy, whose substituent is selected from C6-C 30 Aromatic ring, C5-C 30 Heteroaromatic ring, C1-C8 straight or branched chain alkane, C3-C 10 Alicyclic hydrocarbon, C1-C8 alkoxy, allyl, cyano, halogen, hydrogen or deuterium; Y is NR3, R3 is selected from an electron-withdrawing group or a substituted aromatic group having 5 to 60 ring atoms, wherein the substituent is an electron-withdrawing group selected from the following groups: Where: W is selected from CR 101 or N, and at least one of them is N; R 101 It is selected from H, D, or a linear alkyl group or alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or an aromatic group or heteroaromatic group having 5 to 60 ring atoms.

2. The organic compound according to claim 1, wherein R4 is independently selected from substituted or unsubstituted C6-C 30 Aromatic ring, heteroaromatic ring with 5-30 ring atoms, C1-C8 straight chain or branched alkane, whose substituent is selected from C6-C 30 Aromatic ring, C5-C 30 Heteroaromatic ring, C1-C8 straight or branched chain alkane, C3-C 10 alicyclic hydrocarbon, C1-C8 alkoxy, allyl, cyano, halogen, hydrogen or deuterium.

3. An organic compound, characterized in that The organic compound is selected from the following structures: 。 4. A mixture comprising an organic compound as claimed in any one of claims 1 to 3, and at least one organic functional material, wherein the organic functional material is selected from the group consisting of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, and luminescent body host materials.

5. The mixture according to claim 4, characterized in that The organic functional material is selected from the compound represented by the following general formula (IV): in: A is selected from a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 100 ring atoms; D is an electron-rich group; p is any integer from 1 to 6.

6. A composition comprising an organic compound according to any one of claims 1 to 3 or a mixture according to claim 4 or 5, and at least one organic solvent.

7. An organic electronic device comprising a functional layer, wherein the functional layer comprises at least one organic compound according to any one of claims 1 to 3 or the mixture according to claim 4 or 5.

8. The organic electronic device according to claim 7, characterized in that The organic electronic device is an electroluminescent device and comprises a light-emitting layer. The light-emitting layer comprises an organic compound according to any one of claims 1 to 3 or a mixture according to claim 4 or 5.

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