Boron-containing hydrocarbazole organic compounds and their applications

Abstract

The present application discloses a boron-containing hydrogenated carbazole organic compound and a mixture, a composition and an organic electronic device comprising the boron-containing hydrogenated carbazole organic compound. The boron-containing hydrogenated carbazole organic compound has a structure as shown in the general formula (1): The boron-containing hydrogenated carbazole organic compound is used in an organic electronic device, in particular as a light-emitting material in a light-emitting layer of an organic electronic device, to improve the efficiency and life of the organic electronic device.

Description

Technical Field

[0001] The present application relates to the technical field of luminescent materials, and in particular to a boron-containing hydrogenated carbazole organic compound, and a mixture, a composition and an organic electronic device comprising the boron-containing hydrogenated carbazole organic compound. Background Art

[0002] Organic semiconductor materials offer diverse synthesis, relatively low manufacturing costs, and excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have broad potential for development in optoelectronic devices (such as flat-panel displays and lighting) due to their advantages, including wide viewing angles, fast response times, low operating voltages, and thin panels.

[0003] To improve the luminous efficiency of organic light-emitting diodes (OLEDs), various fluorescent and phosphorescent luminescent material systems have been developed. While OLEDs using fluorescent materials offer high reliability, their internal electroluminescence quantum efficiency (ELQE) is limited to 25% under electrical excitation due to a 1:3 branching ratio between the singlet and triplet excited states of excitons. OLEDs using phosphorescent materials have achieved an EL QE of nearly 100%, but phosphorescent OLEDs exhibit a roll-off effect, whereby the luminous efficiency decreases rapidly with increasing current or brightness, which is particularly detrimental to high-brightness applications.

[0004] To date, conventional phosphorescent materials with practical application have been complexes containing iridium and platinum. However, these raw materials are rare and expensive, and the synthesis of these complexes is complex, resulting in a high cost. To overcome these issues, Adachi proposed the concept of reverse internal conversion, which utilizes organic compounds, rather than metal complexes, to achieve high efficiencies comparable to those of phosphorescent OLEDs. This concept has been implemented through various material combinations, such as: 1) using composite excited-state materials; and 2) using thermally excited delayed fluorescence (TADF) materials. Conventional organic compounds with TADF, however, mostly employ electron-donating (donor) and electron-withdrawing (acceptor) groups linked together, resulting in a complete separation of the electron cloud distributions between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), narrowing the difference (ΔEST) between the singlet (S1) and triplet (T1) states of the organic compound. Conventional blue-emitting TADF materials still lag behind phosphorescent materials in terms of both efficiency and lifetime.

[0005] Therefore, it is necessary to develop new blue light TADF materials to improve the performance of organic electronic devices. Summary of the Invention

[0006] In view of this, the present application provides a blue light fluorescent boron-containing hydrogenated carbazole organic compound as a new type of luminescent material, which is used in organic electronic devices to improve the problems of low luminous efficiency and short life of organic electronic devices.

[0007] The technical solution of this application is as follows:

[0008] A boron-containing hydrogenated carbazole organic compound having a structure as shown in the general formula (1):

[0009]

[0010] in:

[0011] n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3;

[0012] Each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), or a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, or a straight-chain thioalkoxy group having 1 to 20 C atoms, or a branched-chain alkyl group having 3 to 20 C atoms, or a branched-chain alkoxy group having 3 to 20 C atoms, or a branched-chain thioalkoxy group having 3 to 20 C atoms, or a cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a cyclic 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, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, or an isothiocyanate group, a hydroxyl group, a nitro group, a substituted or unsubstituted amine group, -CF3, -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 20 C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

[0013] Adjacent R1s may or may not form a ring with each other;

[0014] Adjacent R2s may form a ring or not;

[0015] Adjacent R3 may or may not form a ring.

[0016] Correspondingly, the present application also provides a mixture comprising the above-mentioned boron-containing hydrogenated carbazole organic compound and at least one organic functional material, wherein the organic functional material is selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials or organic dyes.

[0017] Correspondingly, the present application also provides a composition comprising the above-mentioned boron-containing hydrogenated carbazole organic compound or the above-mentioned mixture, and at least one organic solvent.

[0018] Correspondingly, the present application also provides an organic electronic device, comprising at least one functional layer, wherein the functional layer comprises the above-mentioned boron-containing hydrogenated carbazole organic compound or the above-mentioned mixture, or the functional layer is prepared from the above-mentioned composition.

[0019] Compared with the prior art, the boron-containing hydrogenated carbazole organic compound of the present application has the following beneficial effects:

[0020] The boron-containing hydrocarbazole organic compound of the present invention, formed by fusing a benzene ring with a six-membered aliphatic ring, enhances the overall molecular structure's conjugation and planarity, improving the rigidity and stability of the organic compound. The introduction of the aliphatic ring further enhances the molecule's solubility, making it easier to purify the compound, thereby increasing its purity and thereby extending the luminous efficiency and lifespan of organic electronic devices. Furthermore, the boron-containing hydrocarbazole organic compound of the present invention can be used as a blue light-emitting guest material. When combined with a suitable host material, it can improve the luminous efficiency and lifespan of organic electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0022] Figure 1 This is a schematic structural diagram of an organic electronic device provided in an embodiment of the present application. DETAILED DESCRIPTION

[0023] The following, in conjunction with the accompanying drawings, provides a clear and complete description of the technical solutions in the embodiments of this application. It should be understood that the described embodiments are only some of the embodiments of this application, and not all of them. Based on the embodiments of this application, all other embodiments derived by those skilled in the art without inventive effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are intended only to illustrate and explain this application and are not intended to limit this application. In this application, unless otherwise indicated, directional terms such as "upper" and "lower" generally refer to the upper and lower parts of a device in actual use or operation, specifically the directions of the drawings in the accompanying drawings. Furthermore, in the description of this application, the term "including" means "including but not limited to," the term "plurality" means "two or more," and the term "and / or" includes any and all combinations of one or more of the associated listed items. The various embodiments of this application may be presented in the form of a range. It should be understood that describing in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of this application. Therefore, the range description should be considered to have specifically disclosed all possible subranges and individual numerical values ​​within the range. For example, description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, such as 1, 2, 3, 4, 5, and 6. Furthermore, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.

[0024] In this application, aromatic group, aromatic series and aromatic ring system have the same meaning and can be used interchangeably.

[0025] In the present application, heteroaromatic group, heteroaromatic series and heteroaromatic ring system have the same meaning and can be used interchangeably.

[0026] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0027] In this application, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0028] In the present application, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that the defined group may be substituted by one or more substituents R, wherein R is selected from but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1-20 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silanyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted by substituents acceptable in the art; it is understood that R' and R" in -NR'R" are independently selected from but not limited to: H, deuterium atom, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted by substituents acceptable in the art; it is understood that R' and R" in -NR'R" are independently selected from but not limited to: H, deuterium atom, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, Preferably, R is selected from, but not limited to, a deuterium atom, a cyano group, an isocyano group, a nitro group or a halogen group, an alkyl group containing 1 to 10 carbon atoms, a heterocyclic group containing 3 to 20 ring atoms, an aromatic group containing 6 to 20 ring atoms, or a heteroaromatic group containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to, a deuterium atom, a cyano group, an isocyano group, a nitro group or a halogen group, an alkyl group containing 1 to 10 carbon atoms, a heterocyclic group containing 3 to 10 ring atoms, an aromatic group containing 6 to 20 ring atoms, or a heteroaromatic group containing 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, and a trifluoromethyl group, and the above groups may be further substituted by substituents acceptable in the art.

[0029] In this application, the "number of ring atoms" refers to the number of atoms in the atoms that constitute 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) formed by atoms bonded together 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 also 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 thienyl group is 5.

[0030] In the present application, "aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" refers to an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylenyl, naphthphenyl, fluorenyl, perylene, acenaphthenyl, and their derivatives. It is understood that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g. <10% non-H atoms, such as C, N or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aromatic groups.

[0031] In the present application, "heteroaryl or heteroaromatic group" means that at least one carbon atom on the basis of aryl is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a heteroaryl having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted. Suitable examples include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, triazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyridinyl, oxazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzothiophenyl, benzofuranyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, o-naphthyl, quinoxalinyl, phenanthridinyl, primary pyridyl, quinazolinyl, quinazolinonyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0032] In this application, "alkyl" may refer to a linear, branched and / or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, for example, "C 1-9The term "alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, which can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl at each occurrence. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, tert-butyl, 2-ethylbutyl, 2-pentyl ... Pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantane, and the like.

[0033] In the present application, the substituent abbreviations correspond to: n-normal, sec-secondary, i-iso, t-tertiary, o-ortho, m-meta, p-para, Me methyl, Et ethyl, Pr propyl, Bu butyl, Am n-pentyl, Hx hexyl, Cy cyclohexyl.

[0034] As used herein, "amino" refers to an amine derivative having the structural characteristics of the formula -N(X)2, wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, etc. Non-limiting types of amino groups include -NH2, -N(alkyl), -NH(alkyl), -N(cycloalkyl), -NH(cycloalkyl), -N(heterocyclyl), -NH(heterocyclyl), -N(aryl), -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclyl), -N(cycloalkyl)(heterocyclyl), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0035] In this application, "*" connected to a single bond indicates a connection or fusion site.

[0036] In the present application, when a linking site is not specified in a group, it means that an optional linking site in the group can be used as the linking site.

[0037] In the present application, when no fusion site is specified in a group, it means that any fusion site in the group can be used as the fusion site, and preferably two or more sites in the ortho position in the group are fusion sites.

[0038] In this application, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other, for example The six Rs on the benzene ring may be the same as or different from each other.

[0039] In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example In which R is connected to any substitutable position of the benzene ring, such as express Can be used with The above optional substitutable positions form a ring.

[0040] In the present application, "adjacent groups" means that there is no substitutable site between two substituents.

[0041] In the present application, "two adjacent R's forming a ring with each other" means a ring system formed by two adjacent R's connecting with each other, and the ring system can be selected from aliphatic hydrocarbon rings, aliphatic heterocycles, aromatic hydrocarbon rings or aromatic heterocycles.

[0042] In the embodiments of the present application, the energy level structure of organic materials, triplet energy levels ET, HOMO, and LUMO play a key role. These energy levels are introduced below:

[0043] 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.

[0044] The triplet energy level ET1 of the organic material can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 03W (Gaussian Inc.). The specific simulation method can be found in WO2011141110 or described in the following examples.

[0045] It should be noted that the absolute values ​​of HOMO, LUMO, and ET1 depend on the measurement or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of this application, the values ​​of HOMO, LUMO, and ET1 are based on time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0046] In this application, (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.

[0047] The cyclic alkyl and cycloalkyl groups described herein have the same meaning and can be interchanged.

[0048] The technical solution of this application is as follows:

[0049] A boron-containing hydrogenated carbazole organic compound having a structure as shown in the general formula (1):

[0050]

[0051] in:

[0052] n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3;

[0053] Each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), or a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, or a straight-chain thioalkoxy group having 1 to 20 C atoms, or a branched-chain alkyl group having 3 to 20 C atoms, or a branched-chain alkoxy group having 3 to 20 C atoms, or a branched-chain thioalkoxy group having 3 to 20 C atoms, or a cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a cyclic 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, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, or an isothiocyanate group, a hydroxyl group, a nitro group, a substituted or unsubstituted amine group, -CF3, -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 20 C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

[0054] Adjacent R1s may or may not form a ring with each other;

[0055] Adjacent R2s may form a ring or not;

[0056] Adjacent R3 may or may not form a ring.

[0057] In one embodiment, the “mutual cyclization” is to form a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 10 ring atoms; in a specific embodiment, the “mutual cyclization” is to form a substituted or unsubstituted aromatic group or heteroaromatic group having 6 ring atoms.

[0058] In one embodiment, adjacent R3 groups do not form a ring with each other; further, the boron-containing hydrogenated carbazole organic compound is selected from the structures shown in formulas (2-1) to (2-4):

[0059]

[0060] In one embodiment, adjacent R1s form a ring with each other to form a substituted or unsubstituted aromatic group or heteroaromatic group having 6 ring atoms, or adjacent R1s do not form a ring with each other.

[0061] In one embodiment, adjacent R2s form a ring with each other to form a substituted or unsubstituted aromatic group or heteroaromatic group having 6 ring atoms, or adjacent R2s do not form a ring with each other.

[0062] In one embodiment, the boron-containing hydrocarbazole organic compound is selected from the following structures:

[0063]

[0064] In a specific embodiment, the boron-containing hydrocarbazole organic compound is selected from the structures shown in formulas (3-1) to (3-18):

[0065]

[0066]

[0067] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from -D, or a straight-chain alkyl group having 1 to 10 C atoms, a straight-chain alkoxy group having 1 to 10 C atoms, or a straight-chain thioalkoxy group having 1 to 10 C atoms, or a branched-chain alkyl group having 3 to 10 C atoms, or a branched-chain alkoxy group having 3 to 10 C atoms, or a branched-chain thioalkoxy group having 3 to 10 C atoms, or a cyclic alkyl group having 3 to 10 C atoms, or a cyclic alkoxy group having 3 to 10 C atoms, or a cyclic thioalkoxy group having 3 to 10 C atoms, or a silyl group, or a keto group having 1 to 10 C atoms, or an alkoxy group having 2 to 10 C atoms. carbonyl, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, or an isothiocyanate group, a hydroxyl group, a nitro group, a substituted or unsubstituted amine group, -CF3, -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 10 C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 30 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups.

[0068] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from -D, or a linear alkyl group having 1 to 8 C atoms, or a branched alkyl group having 3 to 8 C atoms, or a cyclic alkyl group having 3 to 8 C atoms, or a silyl group, Or by R 0 A substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a 0 a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.

[0069] in:

[0070] Each occurrence of R4 and R5 is independently selected from a linear alkyl group having 1 to 8 C atoms, a branched alkyl group having 3 to 8 C atoms, a cyclic alkyl group having 3 to 8 C atoms, or a 0 A substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a 0 a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups;

[0071] R 0 Each occurrence of -D is independently selected from a linear alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 3 to 10 C atoms, a silyl group, an aromatic group having 6 to 20 ring atoms, a heteroaromatic group having 6 to 20 ring atoms, or a combination of these groups;

[0072] * indicates the attachment site.

[0073] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from a linear alkyl group having 1 to 8 C atoms, a branched alkyl group having 3 to 8 C atoms, or a cyclic alkyl group having 3 to 8 C atoms, or the following groups:

[0074]

[0075] in:

[0076] Y is selected from CR6R7, NR8, O or S;

[0077] Each occurrence of R6, R7, and R8 is independently selected from -H, -D, or a straight-chain alkyl group having 1 to 10 C atoms, a straight-chain alkoxy group having 1 to 10 C atoms, or a straight-chain thioalkoxy group having 1 to 10 C atoms, or a branched-chain alkyl group having 3 to 10 C atoms, or a branched-chain alkoxy group having 3 to 10 C atoms, or a branched-chain thioalkoxy group having 3 to 10 C atoms, or a cyclic alkyl group having 3 to 10 C atoms, or a cyclic alkoxy group having 3 to 10 C atoms, or a cyclic thioalkoxy group having 3 to 10 C atoms, or a silyl group, or a keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms , or an aryloxycarbonyl group having 7 to 10 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, a substituted or unsubstituted amine group, -CF3, -Cl, -Br, -F, -I, or a substituted or unsubstituted alkenyl group having 1 to 10 C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 20 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups.

[0078] m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2 or 3; m3 is selected from 0, 1, 2, 3, 4 or 5.

[0079] In a specific embodiment, each occurrence of R6, R7, and R8 is independently selected from -H, -D, a straight-chain alkyl group having 1 to 4 C atoms, or a branched-chain alkyl group having 3 to 4 C atoms, or a cyclic alkyl group having 3 to 4 C atoms, or a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.

[0080] In one embodiment, the Selected from the following groups:

[0081]

[0082] wherein: m4 is selected from 0, 1, 2, 3, 4 or 5; m5 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; m6 is selected from 0, 1, 2, 3 or 4; m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0083] In one embodiment, as mentioned above, R 0Each occurrence is independently selected from -D, methyl, ethyl, iPr, tBu, tAm, Et, phenyl, biphenyl, naphthyl, phenanthrenyl, pyridinyl, pyrimidinyl, or phenyl substituted with alkyl having 1 to 6 C atoms.

[0084] In a specific embodiment, each occurrence of R3 is independently selected from methyl, ethyl, iPr, tBu, tAm, Et, or the following groups:

[0085]

[0086]

[0087] In one embodiment, when R3 appears multiple times, it is selected from the same group; preferably, when R3 appears multiple times, it is selected from or a group represented by (A-1) or a group represented by (A-2) or a group represented by (A-3). Preferably, in the structure represented by formula (2-3), (3-5) or (3-9), R3 is selected from or the group represented by (A-1), or the group represented by (A-2), or the group represented by (A-3).

[0088] In a specific embodiment, each occurrence of R1 and R2 is independently selected from a straight-chain alkyl group having 1 to 8 C atoms, or a branched-chain alkyl group having 3 to 8 C atoms; further, each occurrence of R1 and R2 is independently selected from methyl, ethyl, iPr, tBu, tAm, or Et.

[0089] The iPr is isopropyl; tBu is tert-butyl; tAm is tert-amyl; Et is ethyl; and Ph is phenyl.

[0090] As an example, in one embodiment, the boron-containing hydrogenated carbazole organic compound of the present application can be selected from but not limited to any one of the following structures:

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] It is understood that the H in the structural formula of the boron-containing hydrocarbazole organic compound may be further substituted.

[0099] In one embodiment, the boron-containing hydrogenated carbazole organic compound of the present application can be used as an organic functional material in the functional layer of an organic electronic device, particularly in the functional layer of an OLED device. The organic functional material may include, but is not limited to, a hole injection material (HIM), a hole transport material (HTM), an electron transport material (ETM), an electron injection material (EIM), an electron blocking material (EBM), a hole blocking material (HBM), an emitter, a host material (host emitter), and an organic dye.

[0100] In one embodiment, the boron-containing hydrogenated carbazole organic compound of the present application is used in a light-emitting layer. Preferably, the boron-containing hydrogenated carbazole organic compound of the present application is used as a guest material in the light-emitting layer.

[0101] In a specific embodiment, the boron-containing hydrogenated carbazole organic compound according to the present application is used as a blue light emitting material in a light emitting layer.

[0102] The present application further relates to a mixture comprising at least one boron-containing hydrogenated carbazole organic compound as described above and at least another organic functional material. The another organic functional material is selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials, and organic dyes. The luminophores are selected from singlet luminophores (fluorescent luminophores) or triplet luminophores (phosphorescent luminophores) grade organic thermally excited delayed fluorescence materials (TADF materials). Detailed descriptions of various organic functional materials are provided in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated herein by reference. It is understood that the another organic functional material may be a small molecule organic material and a polymer material.

[0103] In one embodiment, the another organic functional material is selected from a host material; further, the another organic functional material is selected from a blue light host material.

[0104] The present application also relates to a composition comprising at least one boron-containing hydrocarbazole organic compound or mixture as described above, and at least one organic solvent.

[0105] The organic solvent is selected from at least one of aromatic or heteroaromatic solvents, ester-based solvents, aromatic ketone-based solvents, aromatic ether-based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefin compounds, borate ester compounds and phosphate ester compounds.

[0106] In at least one embodiment, in the composition, the organic solvent is selected from aromatic or heteroaromatic solvents.

[0107] The aromatic or heteroaromatic based solvent may be selected from, but not limited to, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropyl At least one of biphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, and ethyl 2-furoate.

[0108] The ester-based solvent may be selected from, but not limited to, alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Particularly preferred is at least one of octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate.

[0109] The aromatic ketone-based solvent may be selected from, but not limited to, 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. For example, the derivative may be selected from, but not limited to, at least one of 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, and 2-methylpropiophenone.

[0110] The aromatic ether-based solvent may be selected from, but is not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethyl acetate, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and ethyl-2-naphthyl ether.

[0111] The aliphatic ketone-based solvent can be selected from, but not limited to, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; or an aliphatic ether, for example, at least one of 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, and tetraethylene glycol dimethyl ether.

[0112] It is understood that the organic solvent may be used alone or as a mixed solvent of two or more organic solvents.

[0113] In one embodiment, the composition of the present application includes at least one organic compound or mixture as described above, and at least one organic solvent, and may further include another organic solvent.

[0114] The other organic solvent can be selected from, but not limited to, at least one of 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 (DMSO), tetralin, decalin and indene.

[0115] In one embodiment, the organic solvent suitable for the present application is a solvent having a Hansen solubility parameter within the following range:

[0116] δd (dispersion force) is in the range of 17.0-23.2 MPa1 / 2, especially in the range of 18.5-21.0 MPa1 / 2;

[0117] δp (polar force) is in the range of 0.2-12.5 MPa1 / 2, especially in the range of 2.0-6.0 MPa1 / 2;

[0118] δh (hydrogen bond force) is in the range of 0.9-14.2 MPa1 / 2, especially in the range of 2.0-6.0 MPa1 / 2.

[0119] In one embodiment, the boiling point of the organic solvent used in the composition of the present application should be considered when selecting the solvent. In at least some embodiments, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; more preferably ≥250°C; and most preferably ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging in inkjet printheads.

[0120] It will be appreciated that the organic solvent may be evaporated from the solvent system to form a thin film comprising the organic compound.

[0121] In one embodiment, the composition is a solution. In other embodiments, the composition is a suspension. The solution or suspension may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from, but are not limited to, at least one of a surfactant, a lubricant, a wetting agent, a dispersant, a hydrophobic agent, and an adhesive.

[0122] The composition may also be referred to as ink.

[0123] When used in printing processes, the viscosity and surface tension of ink are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0124] In one embodiment, the surface tension of the ink according to the present application at operating temperature or 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably 22 dyne / cm to 35 dyne / cm; and most preferably 25 dyne / cm to 33 dyne / cm.

[0125] In one embodiment, the viscosity of the ink according to the present application at working temperature or 25° C. ranges from 1 cps to 100 cps; preferably from 1 cps to 50 cps; more preferably from 1.5 cps to 20 cps; and most preferably from 4.0 cps to 20 cps.

[0126] It will be appreciated that inks having the above surface tension and viscosity will facilitate inkjet printing.

[0127] It will be appreciated that the viscosity of the ink can be adjusted by various methods, such as by selecting an appropriate solvent and adjusting the concentration of the functional material in the ink. The inks comprising the boron-containing hydrocarbazole organic compound disclosed herein facilitate adjustment of the viscosity of the printing ink within an appropriate range depending on the printing method employed. Generally, the boron-containing hydrocarbazole organic compound or mixture contained in the compositions disclosed herein comprises a weight percentage of 0.3-30 wt %, preferably 0.5-20 wt %, more preferably 0.5-15 wt %, most preferably 0.5-10 wt %, and most preferably 1-5 wt %.

[0128] The present application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the composition is used to prepare an organic electronic device by a printing or coating method. The printing or coating method can be, but is not limited to, inkjet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slot extrusion coating, etc. Gravure printing, spray printing, and inkjet printing are preferred.

[0129] The present application also relates to the use of the organic compound, mixture or composition described above in an organic electronic device. The specific scheme is as follows:

[0130] An organic electronic device comprises at least one functional layer, wherein the functional layer comprises at least one boron-containing hydrocarbazole organic compound or mixture as described above, or the functional layer is prepared from the above composition.

[0131] Furthermore, the organic electronic device comprises a cathode, an anode and at least one functional layer, wherein the functional layer comprises at least one boron-containing hydrocarbazole organic compound or mixture as described above, or is prepared from the above composition.

[0132] The functional layer may be, but is not limited to, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer, an electron blocking layer, an electron injection layer (EIL), an electron transport layer (ETL), or a hole blocking layer. Preferably, the functional layer is a light-emitting layer.

[0133] The organic electronic device may be, but is 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 (OPD). Particularly preferred are organic electroluminescent devices such as OLEDs, OLEECs, and organic light-emitting field-effect transistors. OLEDs are even more particularly preferred.

[0134] In one embodiment, the organic electronic device includes a substrate and, sequentially stacked on the substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode. The light-emitting layer comprises at least one boron-containing hydrocarbazole organic compound or mixture as described above, or the light-emitting layer is prepared from the composition as described above. It is understood that the structure of the organic electronic device is not limited to this.

[0135] The substrate can be transparent or opaque. A transparent substrate can be used to make a transparent light-emitting device. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer or glass. It is best if the substrate has a smooth surface, and substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics 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 include polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0136] The anode is a hole-injecting electrode, and the anode can easily inject holes into the hole injection layer, the hole transport layer, or the light-emitting layer. The anode may comprise a conductive metal, a conductive metal oxide, or a conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting body 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 and used 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 application. The cathode is an electrode that injects electrons, and the cathode can easily inject electrons into the electron injection layer, or the electron transport layer, or the light-emitting layer. The cathode may comprise a conductive metal or a conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the light-emitting body in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL) or the electron transport layer (ETL) or the 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 cathodes of organic electronic devices may be used as cathode materials of the organic electronic devices of the present application. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material 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.

[0137] The hole injection layer is a layer for promoting the injection of holes from the anode into the light-emitting layer, and the hole injection material is a material that can skillfully receive holes injected from the positive electrode at a low voltage, and preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinone, polyaniline-based and polythiophene-based conductive polymers, etc., but are not limited thereto.

[0138] The hole transport layer can be used to smoothly transport holes. The hole transport material known in the art for the hole transport layer is suitably a material with high hole mobility, which can receive holes transmitted from the anode or the hole injection layer and transfer the holes to the light-emitting layer. Specific examples thereof include, but are not limited to, organic materials based on arylamine, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.

[0139] The electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, a spiroindoloacridine-based compound or a material known in the art may be used.

[0140] Examples of host materials for the light-emitting layer include fused aromatic ring derivatives or heterocyclic compounds. Specifically, examples of fused aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.

[0141] The electron transport layer can be used to smoothly transport electrons. The electron transport material is preferably a material with high electron mobility, which can skillfully receive electrons injected from the negative electrode and transfer the electrons to the light-emitting layer. Specific examples thereof may include, but are not limited to, at least one of an Al complex of 8-hydroxyquinoline, a complex containing Alq3, an organic free radical compound, a hydroxyflavone-metal complex, 8-hydroxyquinoline lithium (Liq), and a benzimidazole-based compound.

[0142] The electron injection layer can be used to smoothly inject electrons. The electron injection material preferably has the ability to transport electrons, has the effect of injecting electrons from the negative electrode, has an excellent effect of injecting electrons into the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the hole injection layer, and also has excellent thin film forming ability. Specific examples include, but are not limited to, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenyl methane, anthrone, and their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

[0143] The hole blocking layer is a layer that blocks holes from reaching the negative electrode and can generally be formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, diazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.

[0144] The light emitting wavelength of the organic electronic device is between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0145] In one embodiment, the organic electronic device described in the present application is a solution-type organic electronic device, and one or more functional layers thereof are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.

[0146] The present application also relates to applications of the organic electronic device according to the present application in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0147] The present application also relates to electronic devices comprising the organic electronic device, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0148] The present application will be described in detail below through specific examples. The following examples are only some examples of the present application and are not limitations of the present application. Specific embodiments

[0150] Example 1

[0151] The synthetic route of organic compound 1 in this example is as follows:

[0152]

[0153] Synthesis of intermediates 1-3

[0154] Under a nitrogen atmosphere, 10 mmol of compound 1-1 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO (dimethyl sulfoxide) was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to give a crude product, which was recrystallized from ethyl acetate to give intermediate 1-3 with a molar weight of 8.43 mmol and a reaction yield of 84.3%. MS (ASAP) = 494.5.

[0155] Synthesis of organic compound 1

[0156] A 250ml three-necked flask was charged with 10mmol of intermediate 1-3 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 1, with a yield of 78.4% and MS (ASAP) = 424.6.

[0157] Example 2

[0158] The synthetic route of organic compound 2 in this embodiment is as follows:

[0159]

[0160] Synthesis of intermediate 2-2

[0161] Under a nitrogen atmosphere, 10 mmol of compound 1-1 and 20 mmol of compound 2-1 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 2-2 with a molar weight of 8.59 mmol and a reaction yield of 85.9%. MS (ASAP) = 594.3.

[0162] Synthesis of organic compound 2

[0163] A 250ml three-necked flask was charged with 10mmol of intermediate 2-2 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 2, with a yield of 59.4% and MS (ASAP) = 524.5.

[0164] Example 3

[0165] The synthetic route of organic compound 3 in this embodiment is as follows:

[0166]

[0167] Synthesis of intermediate 3-3

[0168] Compound 3-1 (10 mmol), compound 3-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 3-3 with a molar weight of 8.33 mmol and a yield of 83.3%. MS (ASAP) = 359.3.

[0169] Synthesis of intermediate 3-4

[0170] Under a nitrogen atmosphere, 10 mmol of intermediate 3-3 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 3-4 with a molar weight of 7.59 mmol and a reaction yield of 75.9%. MS (ASAP) = 661.3.

[0171] Synthesis of organic compound 3

[0172] A 250ml three-necked flask was charged with 10mmol of intermediate 3-4 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 3, with a yield of 71.7% and MS (ASAP) = 591.5.

[0173] Example 4

[0174] The synthetic route of organic compound 4 in this embodiment is as follows:

[0175]

[0176] Synthesis of intermediate 4-2

[0177] Compound 3-1 (10 mmol), compound 4-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 4-2 with a molar weight of 8.75 mmol and a yield of 87.5%. MS (ASAP) = 471.4.

[0178] Synthesis of intermediate 4-3

[0179] Under a nitrogen atmosphere, 10 mmol of intermediate 4-2 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 4-3 with a molar weight of 6.54 mmol and a reaction yield of 65.4%. MS (ASAP) = 773.5.

[0180] Synthesis of organic compound 4

[0181] A 250ml three-necked flask was charged with 10mmol of intermediate 4-3 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 4, with a yield of 69.3% and MS (ASAP) = 703.6.

[0182] Example 5

[0183] The synthetic route of organic compound 5 in this embodiment is as follows:

[0184]

[0185] Synthesis of intermediate 5-3

[0186] Compound 5-1 (10 mmol), compound 5-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 5-3 with a molar weight of 7.18 mmol and a yield of 71.8%. MS (ASAP) = 337.2.

[0187] Synthesis of intermediate 5-4

[0188] Compound 3-1 (10 mmol), intermediate 5-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 5-4 with a molar weight of 8.14 mmol and a yield of 81.4%. MS (ASAP) = 527.3.

[0189] Synthesis of intermediate 5-5

[0190] Under a nitrogen atmosphere, 10 mmol of intermediate 5-4 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 5-5 with a molar weight of 5.96 mmol and a reaction yield of 59.6%. MS (ASAP) = 829.6.

[0191] Synthesis of organic compound 5

[0192] A 250ml three-necked flask was charged with 10mmol of intermediate 5-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. Aqueous sodium carbonate and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 5, with a yield of 70.8% and MS (ASAP) = 759.6.

[0193] Example 6

[0194] The synthetic route of organic compound 6 in this embodiment is as follows:

[0195]

[0196] Synthesis of intermediate 6-2

[0197] Compound 5-1 (10 mmol), compound 6-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 6-2 with a molar weight of 6.54 mmol and a yield of 65.4%. MS (ASAP) = 357.4.

[0198] Synthesis of intermediate 6-3

[0199] Compound 3-1 (10 mmol), intermediate 6-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 6-3 with a molar weight of 7.51 mmol and a yield of 75.1%. MS (ASAP) = 547.5.

[0200] Synthesis of intermediate 6-4

[0201] Under a nitrogen atmosphere, 10 mmol of intermediate 6-3 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 6-4 with a molar weight of 6.71 mmol and a reaction yield of 67.1%. MS (ASAP) = 849.5.

[0202] Synthesis of organic compound 6

[0203] A 250ml three-necked flask was charged with 10mmol of intermediate 6-4 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 6, with a yield of 69.4% and MS (ASAP) = 779.6.

[0204] Example 7

[0205] The synthetic route of organic compound 7 in this embodiment is as follows:

[0206]

[0207] Synthesis of intermediate 7-3

[0208] Compound 7-1 (10 mmol), compound 7-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 7-3 with a molar weight of 6.32 mmol and a yield of 63.2%. MS (ASAP) = 329.3.

[0209] Synthesis of intermediate 7-4

[0210] Compound 3-1 (10 mmol), intermediate 7-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 7-4 with a molar weight of 8.83 mmol and a yield of 88.3%. MS (ASAP) = 519.5.

[0211] Synthesis of intermediate 7-5

[0212] Under a nitrogen atmosphere, 10 mmol of intermediate 7-4 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 7-5 with a molar weight of 6.43 mmol and a reaction yield of 64.3%. MS (ASAP) = 821.4.

[0213] Synthesis of organic compound 7

[0214] A 250ml three-necked flask was charged with 10mmol of intermediate 7-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 7, with a yield of 54.3% and MS (ASAP) = 751.6.

[0215] Example 8

[0216] The synthetic route of organic compound 8 in this embodiment is as follows:

[0217]

[0218] Synthesis of intermediate 8-3

[0219] Compound 8-1 (10 mmol), compound 8-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 8-3 with a molar weight of 7.48 mmol and a yield of 74.8%. MS (ASAP) = 401.4.

[0220] Synthesis of intermediate 8-4

[0221] Compound 3-1 (10 mmol), intermediate 8-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 8-4 with a molar weight of 8.19 mmol and a yield of 81.9%. MS (ASAP) = 591.5.

[0222] Synthesis of intermediate 8-5

[0223] Under a nitrogen atmosphere, 10 mmol of intermediate 8-4 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 8-5 with a molar weight of 6.32 mmol and a reaction yield of 63.2%. MS (ASAP) = 893.5.

[0224] Synthesis of organic compound 8

[0225] A 250ml three-necked flask was charged with 10mmol of intermediate 8-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 8, with a yield of 68.4% and MS (ASAP) = 823.7.

[0226] Example 9

[0227] The synthetic route of organic compound 9 in this embodiment is as follows:

[0228]

[0229] Synthesis of intermediate 9-3

[0230] Compound 9-1 (10 mmol), compound 9-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 9-3 with a molar weight of 8.56 mmol and a yield of 85.6%. MS (ASAP) = 499.7.

[0231] Synthesis of intermediate 9-4

[0232] Compound 3-1 (10 mmol), intermediate 9-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 9-4 with a molar weight of 7.42 mmol and a yield of 74.2%. MS (ASAP) = 689.6.

[0233] Synthesis of intermediate 9-5

[0234] Under a nitrogen atmosphere, 10 mmol of intermediate 9-4 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 9-5 with a molar weight of 5.48 mmol and a reaction yield of 54.8%. MS (ASAP) = 991.7.

[0235] Synthesis of organic compound 9

[0236] A 250ml three-necked flask was charged with 10mmol of intermediate 9-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 9, with a yield of 50.4% and MS (ASAP) = 921.6.

[0237] Example 10

[0238] The synthetic route of the organic compound 10 in this embodiment is as follows:

[0239]

[0240] Synthesis of intermediate 10-3

[0241] Compound 10-1 (10 mmol), compound 10-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 10-3 with a molar weight of 7.41 mmol and a yield of 74.1%. MS (ASAP) = 365.5.

[0242] Synthesis of intermediate 10-4

[0243] Compound 3-1 (10 mmol), intermediate 10-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 10-4 with a molar weight of 8.46 mmol and a yield of 84.6%. MS (ASAP) = 555.3.

[0244] Synthesis of intermediate 10-5

[0245] Under a nitrogen atmosphere, 10 mmol of intermediate 10-4 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 10-5 with a molar weight of 3.89 mmol and a reaction yield of 38.9%. MS (ASAP) = 857.4.

[0246] Synthesis of organic compound 10

[0247] A 250ml three-necked flask was charged with 10mmol of intermediate 10-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 10, with a yield of 79.6% and MS (ASAP) = 787.5.

[0248] Example 11

[0249] The synthetic route of the organic compound 11 in this example is as follows:

[0250]

[0251] Synthesis of intermediate 11-3

[0252] Compound 11-1 (20 mmol), compound 11-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The resulting mixture was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 11-3 with a molar weight of 8.45 mmol and a yield of 84.5%. MS (ASAP) = 390.4.

[0253] Synthesis of intermediate 11-4

[0254] Under a nitrogen atmosphere, 10 mmol of intermediate 11-3 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 11-4 with a molar weight of 6.58 mmol and a reaction yield of 65.8%. MS (ASAP) = 692.5.

[0255] Synthesis of organic compound 11

[0256] A 250ml three-necked flask was charged with 10mmol of intermediate 11-4 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 11, with a yield of 46.3% and MS (ASAP) = 622.8.

[0257] Example 12

[0258] The synthetic route of the organic compound 12 in this example is as follows:

[0259]

[0260] Synthesis of intermediate 12-2

[0261] Compound 12-1 (20 mmol), compound 11-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The resulting mixture was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 12-2 with a molar weight of 7.05 mmol and a yield of 70.5%. MS (ASAP) = 526.3.

[0262] Synthesis of intermediate 12-3

[0263] Under a nitrogen atmosphere, 10 mmol of intermediate 12-2 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 12-3 with a molar weight of 7.49 mmol and a reaction yield of 74.9%. MS (ASAP) = 828.4.

[0264] Synthesis of organic compound 12

[0265] A 250ml three-necked flask was charged with 10mmol of intermediate 12-3 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 12, with a yield of 55.7% and MS (ASAP) = 758.8.

[0266] Example 13

[0267] The synthetic route of the organic compound 13 in this example is as follows:

[0268]

[0269] Synthesis of intermediate 13-3

[0270] Intermediate 13-1 (10 mmol) and intermediate 13-2 (10 mmol) were dissolved in a mixture of 1,4-dioxane and water (2 1 / 2 ml). Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium 0.1 mmol) and potassium carbonate (30 mmol) were added. The mixture was stirred at 80°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was mostly removed by rotary evaporation. The mixture was then extracted and washed with water. The organic phase was purified by column chromatography and recrystallized to afford intermediate 13-3 with a molar weight of 8.46 mmol and a yield of 84.6%. MS (ASAP) = 407.4.

[0271] Synthesis of intermediate 13-5

[0272] Intermediate 13-3 (10 mmol) and compound 13-4 (10 mmol) were dissolved in a mixture of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. The mixture was stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was mostly removed by rotary evaporation, and the resulting mixture was extracted and washed with water. The organic phase was purified by column chromatography and recrystallized to afford Intermediate 13-5 with a molar weight of 6.98 mmol and a yield of 69.8%. MS (ASAP) = 496.1.

[0273] Synthesis of intermediate 13-6

[0274] Under a nitrogen atmosphere, 10 mmol of intermediate 13-5 and 20 mmol of compound 1-2 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 13-6 with a molar weight of 5.91 mmol and a reaction yield of 59.1%. MS (ASAP) = 798.5.

[0275] Synthesis of organic compound 13

[0276] A 250ml three-necked flask was charged with 10mmol of intermediate 13-6 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 32mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 13, with a yield of 29.3% and MS (ASAP) = 772.7.

[0277] Example 14

[0278] The synthetic route of organic compound 14 in this example is as follows:

[0279]

[0280] Synthesis of intermediate 14-2

[0281] Under a nitrogen atmosphere, 10 mmol of compound 1-1 and 20 mmol of compound 14-1 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 14-2 with a molar weight of 8.11 mmol and a reaction yield of 81.1%. MS (ASAP) = 606.8.

[0282] Synthesis of organic compound 14

[0283] A 250ml three-necked flask was charged with 10mmol of intermediate 14-2 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 14, with a yield of 73.1% and MS (ASAP) = 536.9.

[0284] Example 15

[0285] The synthetic route of organic compound 15 in this example is as follows:

[0286]

[0287] Synthesis of intermediate 15-2

[0288] Compound 15-1 (20 mmol) and compound 11-2 (10 mmol) were dissolved in a mixture of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. The mixture was stirred at 80°C for 3 h under a nitrogen atmosphere. After cooling, the solvent was mostly removed by rotary evaporation. The mixture was then extracted and washed with water. The organic phase was purified by column chromatography and recrystallized to obtain intermediate 15-2 with a molar weight of 7.35 mmol and a yield of 73.5%. MS (ASAP) = 484.7.

[0289] Synthesis of intermediate 15-4

[0290] Under nitrogen atmosphere, 10 mmol of intermediate 15-2 and 20 mmol of compound 15-3 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 15-4 with a molar weight of 6.39 mmol and a reaction yield of 63.9%. MS (ASAP) = 871.3.

[0291] Synthesis of organic compound 15

[0292] A 250ml three-necked flask was charged with 10mmol of intermediate 15-4 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 15, with a yield of 53.1% and MS (ASAP) = 800.8.

[0293] Example 16

[0294] The synthetic route of organic compound 16 in this example is as follows:

[0295]

[0296] Synthesis of intermediate 16-2

[0297] Compound 16-1 (20 mmol) and compound 11-2 (10 mmol) were dissolved in a mixture of 1,4-dioxane and water (2 1 / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. The mixture was stirred at 80°C for 3 h under a nitrogen atmosphere. After cooling, the solvent was mostly removed by rotary evaporation. The mixture was then extracted and washed with water. The organic phase was purified by column chromatography and recrystallized to obtain intermediate 16-2 with a molar weight of 7.18 mmol and a yield of 71.8%. MS (ASAP) = 524.9.

[0298] Synthesis of intermediate 16-3

[0299] Under nitrogen atmosphere, 10 mmol of intermediate 16-2 and 20 mmol of compound 14-1 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 16-3 with a molar weight of 6.15 mmol and a reaction yield of 61.5%. MS (ASAP) = 938.4.

[0300] Synthesis of organic compound 16

[0301] A 250ml three-necked flask was charged with 10mmol of intermediate 16-3 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 16, with a yield of 57.5% and MS (ASAP) = 868.7.

[0302] Example 17

[0303] The synthetic route of organic compound 17 in this example is as follows:

[0304]

[0305] Synthesis of intermediate 17-3

[0306] Compound 17-1 (10 mmol), compound 17-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 12 h. After cooling, the solvent was removed by rotary evaporation. The resulting mixture was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 17-3 with a molar weight of 7.27 mmol and a yield of 72.7%. MS (ASAP) = 259.8.

[0307] Synthesis of intermediate 17-4

[0308] Compound 3-1 (10 mmol), intermediate 17-3 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 17-4 with a molar weight of 7.59 mmol and a yield of 75.9%. MS (ASAP) = 449.9.

[0309] Synthesis of intermediate 17-6

[0310] Under nitrogen atmosphere, 10 mmol of intermediate 17-4 and 20 mmol of compound 17-5 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 17-6 with a molar weight of 5.89 mmol and a reaction yield of 58.9%. MS (ASAP) = 779.6.

[0311] Synthesis of organic compound 17

[0312] A 250ml three-necked flask was charged with 10mmol of intermediate 17-6 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 17, with a yield of 64.5% and MS (ASAP) = 710.1.

[0313] Example 18

[0314] The synthetic route of organic compound 18 in this example is as follows:

[0315]

[0316] Synthesis of intermediate 18-2

[0317] Compound 3-1 (10 mmol), compound 18-1 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 18-2 with a molar weight of 8.25 mmol and a yield of 82.5%. MS (ASAP) = 385.5.

[0318] Synthesis of intermediate 18-3

[0319] Under nitrogen atmosphere, 10 mmol of intermediate 18-2 and 20 mmol of compound 15-3 were added to a dry three-necked flask, 100 ml of DMSO was poured as a solvent, and dry Cs2CO3 was added as a base. The reaction was carried out at 120°C for 8 hours and monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, water and dichloromethane were added in sequence, the reaction solution was washed with water several times, and the aqueous phase was extracted with dichloromethane several times. The organic phases were combined, dried over anhydrous Na2CO3, filtered, and the reaction solution was spin-dried to obtain a crude product, which was recrystallized from ethyl acetate to obtain intermediate 18-3 with a molar weight of 7.59 mmol and a reaction yield of 75.9%. MS (ASAP) = 771.7.

[0320] Synthesis of organic compound 18

[0321] A 250ml three-necked flask was charged with 10mmol of intermediate 18-3 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 18, with a yield of 54.2% and MS (ASAP) = 701.7.

[0322] Example 19

[0323] The synthetic route of organic compound 19 in this example is as follows:

[0324]

[0325] Synthesis of intermediate 19-3

[0326] Compound 19-1 (10 mmol), compound 19-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 19-3 with a molar weight of 7.27 mmol and a yield of 72.7%. MS (ASAP) = 408.1.

[0327] Synthesis of intermediate 19-5

[0328] Intermediate 19-3 (10 mmol), compound 19-4 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain Intermediate 19-5 with a molar weight of 8.11 mmol and a yield of 81.1%. MS (ASAP) = 634.5.

[0329] Synthesis of organic compound 19

[0330] A 250ml three-necked flask was charged with 10mmol of intermediate 19-5 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 19, with a yield of 45.9% and MS (ASAP) = 608.1.

[0331] Example 20

[0332] The synthetic route of the organic compound 20 in this embodiment is as follows:

[0333]

[0334] Synthesis of Intermediate 20-3

[0335] Compound 20-1 (10 mmol), compound 20-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fraction was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 20-3 with a molar weight of 8.35 mmol and a yield of 83.5%. MS (ASAP) = 491.4.

[0336] Synthesis of Intermediate 20-4

[0337] Intermediate 20-3 (10 mmol), compound 1-2 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain intermediate 20-4 with a molar weight of 6.52 mmol and a yield of 65.2%. MS (ASAP) = 582.7.

[0338] Synthesis of Intermediate 20-6

[0339] Intermediate 20-4 (10 mmol), compound 20-5 (10 mmol), Pd(dba)2 (0.1 mmol), TTBP (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was removed by rotary evaporation. The liquid fractions were extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, and purified by column chromatography to obtain Intermediate 20-6 with a molar weight of 6.17 mmol and a yield of 61.7%. MS (ASAP) = 767.9.

[0340] Synthesis of organic compound 20

[0341] A 250ml three-necked flask was charged with 10mmol of intermediate 20-6 and 100ml of dry tert-butylbenzene. The mixture was cooled to -30°C under a nitrogen atmosphere, and 21mmol of t-BuLi in n-hexane was added dropwise. The temperature was raised to 60°C and the reaction was allowed to proceed for 2 hours. The n-hexane solvent was then evaporated under reduced pressure. The reaction solution was cooled again to -30°C, and 21mmol of boron tribromide solution was added. The mixture was heated to room temperature and stirred for 0.5 hours. The reaction solution was then cooled to 0°C and 42mmol of N,N-diisopropylethylamine was added. After the addition was complete, the mixture was heated to room temperature and stirred. The temperature was then raised to 120°C and stirred for 3 hours. The reaction solution was then cooled to room temperature. The reaction was quenched by the addition of aqueous sodium carbonate and ethyl acetate. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column chromatography to obtain a pure product. The product was recrystallized from toluene and ethyl acetate to obtain a light yellow solid powder, i.e., organic compound 20, with a yield of 37.9% and MS (ASAP) = 741.9.

[0342] Comparative Example

[0343] The organic compound in this comparative example is BD-Ref1, and its chemical structure is as follows:

[0344]

[0345] Energy level calculation of organic compounds

[0346] The energy levels HOMO, LUMO, T1 and S1 of the organic compounds of Examples 1-20 and Comparative Examples were calculated. Specifically, TD-DFT (time-dependent density functional theory) was used through Gaussian 09W (Gaussian Inc.). The specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet) was used to optimize the molecular geometry. Then, the energy structure of the organic molecule was calculated by the TD-DFT (time-dependent density functional theory) method using "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, and S1 and T1 were used directly:

[0347] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206;

[0348] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385.

[0349] HOMO, LUMO, T1, and S1 are calculated directly using Gaussian 09W, in Hartree units. See Table 1 below for the results.

[0350] Table 1:

[0351] Compound HOMO[eV] LUMO[eV] T1[eV] S1[eV] Example 1 Organic Compound 1 -5.45 -2.70 2.33 2.95 Example 2 Organic Compounds 2 -5.35 -2.68 2.35 3.04 Example 3 Organic Compound 3 -5.30 -2.54 2.41 2.95 Example 4 Organic Compound 4 -5.35 -2.54 2.38 2.93 Example 5 Organic compounds 5 -5.29 -2.51 2.39 3.07 Example 6 Organic Compound 6 -5.15 -2.41 2.43 3.05 Example 7 Organic compound 7 -5.28 -2.49 2.41 2.97 Example 8 Organic compounds 8 -5.17 -2.45 2.48 3,05 Example 9 Organic compounds 9 -5.40 -2.63 2.41 3.04 Example 10 Organic Compound 10 -5.29 -2.56 2.38 3.01 Example 11 Organic Compound 11 -5.21 -2.51 2.37 3.09 Example 12 Organic Compound 12 -5.24 -2.46 2.39 2.93 Example 13 Organic Compound 13 -5.18 -2.47 2.35 3.06 Example 14 Organic Compound 14 -5.12 -2.38 2.41 3.01 Example 15 Organic Compound 15 -5.15 -2.41 2.35 2.96 Example 16 Organic Compound 16 -5.20 -2.45 2.32 2.98 Example 17 Organic compound 17 -5.22 -2.49 2.46 2.93 Example 18 Organic Compound 18 -5.15 -2.51 2.38 2.98 Example 19 Organic compound 19 -5.14 -2.43 2.41 2.96 Example 20 Organic Compound 20 -5.16 -2.51 2.43 3.05 Comparative Example BD-Ref1 -5.17 -2.32 2.31 2.81

[0352] As can be seen from Table 1, the organic compounds of the present application have suitable HOMO, LUMO, T1 and S1 energy levels and can be used as blue light guest materials.

[0353] Preparation and characterization of OLED devices

[0354] In the OLED device of this embodiment, ITO is used as the anode, PEDOT (polyethylenedioxythiophene, Clevios TM AI4083) is used as a hole injection layer material, PVK (Sigma Aldrich, average Mn 25,000-50,000) is used as a hole transport material, BH is used as a host material of the light-emitting material, the organic compounds in Examples 1-20 and the comparative examples are used as guest materials (BD) of the light-emitting material, ET and Liq are used as electron transport materials, and Al is used as a cathode. The device structure is ITO / PEDOT / PVK / BH:BD / ET:Liq / Al.

[0355] The chemical structural formulas of BH, ET and Liq are as follows:

[0356]

[0357] The above materials BH, ET, and Liq are all commercially available, or their synthesis methods are all prior art.

[0358] The schematic diagram of OLED device is as follows Figure 1 10 is a substrate, 20 is an anode, 30 is a hole injection layer (HIL), 40 is a hole transport layer (HTL), 50 is a light emitting layer, 60 is an electron transport layer (ETL), and 70 is a cathode.

[0359] The following describes in detail the preparation process of an OLED device using the above materials through specific examples.

[0360] Device Example 1

[0361] The method for preparing an OLED device in this embodiment includes the following steps:

[0362] 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;

[0363] b. HIL (hole injection layer, 40 nm): PEDOT (polyethylenedioxythiophene, Clevios TM AI4083) was spin-coated as the HIL in a clean room and treated on a hot plate at 180 °C for 10 min;

[0364] c. HTL (hole transport layer, 20 nm): PVK solution (Sigma Aldrich, average Mn 25,000-50,000) was spin-coated in a nitrogen glove box. The solution was 5 mg / ml of PVK in toluene solvent and then heated on a hot plate at 180°C for 60 min.

[0365] d. EML (organic light-emitting layer, 40 nm): The EML was formed by spin coating in a nitrogen glove box using a 15 mg / ml solution of methyl benzoate containing different host and guest materials (host-guest weight ratio of 95:5). The EML was then heated on a 140°C hot plate for 10 minutes. The host material was BH, and the guest was the organic compound of Example 1. All other embodiments were the same.

[0366] e. Electron transport layer and cathode: The heat-treated substrate was transferred to a vacuum chamber, and then ET and Liq were placed in different evaporation units under high vacuum (1×10 -6 mbar) and co-deposited them at a ratio of 50 wt % to form a 20 nm electron transport layer on the light-emitting layer, and then deposited an Al cathode with a thickness of 100 nm;

[0367] f. Packaging: Packaging with UV curable resin in a nitrogen glove box.

[0368] Device Examples 2-20

[0369] The device is basically the same as the device embodiment 1, except that the guest materials of the light-emitting layers of the device embodiments 2-20 are respectively selected from the organic compounds of embodiments 2-20.

[0370] Device Comparison

[0371] It is basically the same as the device embodiment 1, except that the guest material of the light-emitting layer of the device comparative example is BD-Ref1.

[0372] Performance testing and results

[0373] The current-voltage (JV) characteristics of the OLED devices of device examples 1-20 and the device comparison example were tested using a characterization device, and important parameters such as color coordinates, voltage, luminous efficiency CE, and lifespan LT90 were recorded.

[0374] Table 1:

[0375]

[0376]

[0377] From Table 1 we can see that:

[0378] Compared with the blue OLED device prepared using the organic compound of the comparative example, the blue OLED device prepared using the organic compound of Examples 1-20 has better color coordinates.

[0379] The luminous efficiency of the blue OLED devices prepared by using the organic compounds of Examples 1-20 as the guest material in the light-emitting layer is in the range of 5.3-6.4 cd / A, which has a more excellent luminous efficiency.

[0380] Blue OLED devices prepared using the organic compounds of Examples 1, 3, 11, and 12 as guest materials in the light-emitting layer all exhibited luminous efficiencies ranging from 6.0 to 6.4 cd / A and lifetimes of approximately 160 to 170 hours, demonstrating the highest luminous efficiency and lifetime. Possible reasons for this are: the device luminous efficiency and lifetime of Example 1 surpass those of the other examples, demonstrating that the fundamental structure inherently possesses excellent properties, making it suitable as a blue light-emitting guest material; while Examples 3, 11, and 12 introduce diphenylamine and diisopropylamine groups at the para and meta positions of the boron atom within the molecular structure, imparting a large triarylamine structure to the organic compound molecules, slightly improving the luminous efficiency and lifetime of the devices compared to Example 1; and the introduction of hydrogenated carbazole enhances the solubility of the organic compound molecules, facilitating purification of the organic compound, thereby effectively increasing the compound purity and, consequently, the luminous efficiency and lifetime of the devices.

[0381] In addition, compared with the blue OLED device prepared using the organic compound of the comparative example as the guest material in the light-emitting layer, the lifespan of the blue OLED device prepared using the organic compounds of Examples 1-20 as the guest material in the light-emitting layer is generally increased by 50%-70%.

[0382] The boron-containing hydrocarbazole organic compound of the present invention, formed by fusing a benzene ring with a six-membered aliphatic ring, enhances the overall molecular structure's conjugation and planarity, improving the rigidity and stability of the organic compound. The introduction of the aliphatic ring further enhances the molecule's solubility, making it easier to purify the compound, thereby increasing its purity and thereby extending the luminous efficiency and lifespan of organic electronic devices. Furthermore, the boron-containing hydrocarbazole organic compound of the present invention can be used as a blue light-emitting guest material. When combined with a suitable host material, it can improve the luminous efficiency and lifespan of organic electronic devices.

[0383] The organic compounds, mixtures, compositions and organic electronic devices provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core ideas of the present application. At the same time, for those skilled in the art, according to the ideas of the present application, there may be changes in the specific implementation methods and application scopes. In summary, the contents of this specification should not be understood as limiting the present application.

Claims

1. A boron-containing hydrocarbazole organic compound, characterized in that: It has the structure shown in the general formula (1): （1） in: n1 is selected from 0, 1, 2 or 3; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2 or 3; Each occurrence of R1 and R2 is independently selected from methyl, ethyl, iPr, tBu, tAm, Et or ; Each occurrence of R3 is independently selected from -D, 、 、 or ; wherein R4 and R5 are each independently selected from a linear alkyl group having 1 to 8 C atoms, a branched alkyl group having 3 to 8 C atoms, a phenyl group, a naphthyl group, or a ,or ,or ,or ,or , or a combination of these groups; Y is selected from CR6R7, NR8, O or S; R6, R7, R8, each occurrence, are independently selected from -H, -D, or straight chain alkyl having 1 to 10 C atoms, or branched chain alkyl having 3 to 10 C atoms, or phenyl; m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2 or 3; m3 is selected from 0, 1, 2, 3, 4 or 5; Indicates the attachment site.

2. The boron-containing hydrocarbazole organic compound according to claim 1, wherein The boron-containing hydrocarbazole organic compound is selected from the structures shown in formulas (2-1) to (2-4): 。 3. The boron-containing hydrocarbazole organic compound according to claim 1, wherein The structure of the boron-containing hydrocarbazole organic compound is shown below: 。 4. The boron-containing hydrocarbazole organic compound according to claim 1, wherein The boron-containing hydrocarbazole organic compound is selected from the structures shown in formulas (3-1) to (3-18): 。 5. The boron-containing hydrocarbazole organic compound according to claim 1, 2, 3 or 4, wherein: Each occurrence of R3 is independently selected from methyl, ethyl, iPr, tBu, tAm, Et, or the following groups: ； in: Indicates the attachment site.

6. The boron-containing hydrocarbazole organic compound according to claim 1, wherein The boron-containing hydrocarbazole organic compound is selected from the following structures: 。 7. A mixture, characterized in that: The mixture comprises the boron-containing hydrogenated carbazole organic compound according to any one of claims 1 to 6 and at least one organic functional material, wherein the organic functional material is selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminophore, a host material or an organic dye.

8. A composition, characterized in that: The composition comprises the boron-containing hydrocarbazole organic compound according to any one of claims 1 to 6 or the mixture according to claim 7, and at least one organic solvent.

9. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer comprises the boron-containing hydrogenated carbazole organic compound according to any one of claims 1 to 6, or the mixture according to claim 7, or the functional layer is prepared from the composition according to claim 8.

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