Organic compound, mixture, composition, light extraction layer material and organic electronic device

Abstract

The present invention provides an organic compound, a mixture, a composition, a light extraction layer material and an organic electronic device. The structure of the organic compound is shown in the general formula (1), and the organic compound can be used as a light extraction layer material in an organic electroluminescent device to improve the light extraction efficiency of the device.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescence, and in particular to an organic compound, a mixture, a composition, a light extraction layer material and an organic electronic device. Background Art

[0002] Organic electroluminescent display devices are a type of self-luminous display device that generates excitons through the transfer and recombination of carriers between various functional layers, and emits light through organic compounds or metal complexes with high quantum efficiency. It has the characteristics of self-luminescence, high brightness, high efficiency, high contrast, and high responsiveness.

[0003] In recent years, the luminous efficiency of organic light-emitting diodes (OLEDs) has been greatly improved, but its internal quantum efficiency has approached the theoretical limit. Therefore, improving the light extraction efficiency has become an effective means to further improve the stability and current efficiency of the device, such as the accumulation of metal complexes in the emission layer and the matching of the refractive index between the functional layers.

[0004] OLED is a light-emitting device with a top-emitting structure. For such a light-emitting device, when the light emitted by the light-emitting layer enters other films, if the incident angle is above a certain angle, total reflection will occur at the interface between the light-emitting layer and other films, resulting in the light emitted by the light-emitting layer being unable to exit the device, resulting in only a portion of the emitted light being able to be used. In recent years, in order to improve the efficiency of light extraction, traditional technology has adopted a light-emitting device in which a "covering layer" with a high refractive index is arranged on the outside of a semi-transparent electrode with a low refractive index. For example, in 2003, Riel et al. evaporated ZnSe, an inorganic compound with a high refractive index (n=2.6), on the cathode, and used the difference in refractive index between the functional layers to improve the light extraction efficiency. However, due to the high evaporation temperature and slow evaporation rate of inorganic materials, this type of compound has not been widely used in organic electroluminescent devices. Summary of the invention

[0005] Based on this, the present invention provides an organic compound, which can be used as a light extraction layer material in an organic electroluminescent device to improve the light extraction efficiency of the device.

[0006] The present invention is achieved through the following technical solutions:

[0007] An organic compound, the structure of which is shown in general formula (1):

[0008]

[0009] in:

[0010] X1 and X2 are independently selected from O, S or NR1;

[0011] L1 and L2 are independently selected from: a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;

[0012] M1 and M2 are independently selected from: a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, and a substituted or unsubstituted amine group;

[0013] Each occurrence of R1 is independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, branched alkyl having 3 to 20 C atoms, alkenyl having 2 to 20 C atoms, cyclic alkyl having 3 to 20 C atoms, substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms.

[0014] The present invention also provides a mixture, which comprises the organic compound as described above 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, luminescent bodies or host materials.

[0015] The present invention also provides a composition, comprising the organic compound or the mixture as described above, and at least one organic solvent.

[0016] The present invention further provides a light extraction layer material, wherein the light extraction layer material comprises the organic compound as described above or the mixture as described above or is prepared from the composition as described above.

[0017] The present invention also provides an organic electronic device, which comprises the organic compound as described above, the mixture as described above, or is prepared from the composition as described above.

[0018] Compared with the prior art, the organic compound of the present invention has the following beneficial effects:

[0019] The organic compound described in the present invention has high absorption in the ultraviolet band, that is, the extinction coefficient in the ultraviolet band (<400nm) is high, which can resist the damage of external high-energy light to the inside of the device and avoid the adverse effects of harmful light on the device material, while the absorption in the visible light band is weak, which is reflected in the extinction coefficient close to 0 in the visible light range (>430nm), and has a high transmittance to visible light, and has a high refractive index in the visible light range and a small difference, thereby ensuring a better light extraction effect. At the same time, the organic compound described in the present invention also has a high glass transition temperature and thermal decomposition temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 A schematic diagram of the structure of a light-emitting device provided for one embodiment of the present invention; in the figure, 1 is a substrate, 2 is an anode, 3a is a hole injection layer, 3b is a hole transport layer, 3c is a light-emitting layer, 3d is an electron transport layer, 3e is an electron injection layer, 4 is a cathode, and 5 is a light extraction layer. DETAILED DESCRIPTION

[0021] For ease of understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. Preferred embodiments of the present invention are provided in the embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0023] In the present invention, composition and printing ink, or ink have the same meaning and can be interchanged.

[0024] In the present invention, aromatic group, aromatic series and aromatic ring system have the same meaning and can be interchanged.

[0025] In the present invention, heteroaromatic group, heteroaromatic series and heteroaromatic ring system have the same meaning and can be interchanged.

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

[0027] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R1, then R1 can be independently selected from different groups.

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

[0029] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below 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] "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 aromatic group having 6 to 40 ring atoms" refers to an aromatic group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aromatic group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aromatic group having 6 to 14 ring atoms, and the aromatic group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and derivatives thereof. It is understandable 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] "Heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, 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 group is optionally further substituted, and suitable examples include but are not limited to: thienyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzothienyl, benzofuranyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0032] In the present invention, "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, such as "C 1-9"Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl 2-Hexyldecyl, 2-octyldecyl, 2-undecyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, 2-undecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-tridecyl, 2-tetradecyl, 2-pentadecyl, 2-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, 2-heptadecyl, 2-octylhexadecyl, 2-octadecyl, 2-octadecyl, 2-nonadecyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, 2-heneicosyl, 2-heneicosyl, 2-heconicosyl, 2-docosyl, 2-tricosyl, 2-tetracosyl, 2-pentacosyl, 2-hexacosyl, 2-heptacosyl, 2-octacosyl, 2-nonacosyl, 2-triacontyl, etc.

[0033] In the present invention, 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] "Amine" refers to an amine derivative having the structural features 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 amines 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 the present invention, "*" connected to a single bond indicates a connection or fusion site;

[0036] In the present invention, when a linking site is not specified in a group, it means that any linking site in the group can be used as a linking site;

[0037] In the present invention, when the fusion site is not specified in the 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 the present invention, when the same group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. 6 R on the benzene ring 1 May be the same as or different from each other.

[0039] In the present invention, 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; express Can be used with The benzene ring can be fused at any position.

[0040] According to the present invention, the cyclic alkyl or cycloalkyl group has the same meaning and can be interchanged.

[0041] In the present invention, "adjacent groups" means that there is no substitutable site between two substituents.

[0042] The present invention provides an organic compound, the structure of which is shown in the general formula (1):

[0043]

[0044] in:

[0045] X1 and X2 are independently selected from O, S or NR1;

[0046] L1 and L2 are independently selected from: a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;

[0047] M1 and M2 are independently selected from: a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, and a substituted or unsubstituted amine group;

[0048] Each occurrence of R1 is independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, branched alkyl having 3 to 20 C atoms, alkenyl having 2 to 20 C atoms, cyclic alkyl having 3 to 20 C atoms, substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms.

[0049] In a specific example, the substituent R in the "substituted or unsubstituted" is preferably selected from an alkyl group having 1 to 10 C atoms, an aryl group having 6 to 10 ring atoms, or a heteroaryl group having 6 to 10 ring atoms.

[0050] In one embodiment, each occurrence of R1 is independently selected from: -H, -D, 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 phenyl group, a biphenyl group, a terphenyl group, a pyrimidinyl group, a pyrimidinyl group, a triazinyl group, a naphthyl group, a quinolyl group, or an isoquinolyl group.

[0051] In a specific example, X1 and X2 are independently selected from O or S.

[0052] Furthermore, the structure of the organic compound is shown in the general formula (2-1) or (2-2):

[0053]

[0054] In one embodiment, the Select from the following structures:

[0055]

[0056] Wherein: * indicates the connection site.

[0057] In a specific example, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.

[0058] In a specific example, L1 and L2 are independently selected from a single bond or any of the following groups:

[0059]

[0060] in:

[0061] Each occurrence of V1 is independently selected from CR2 or N;

[0062] Y1 is selected from NR3, CR4R5, SiR4R5, O, S, S=O or SO2;

[0063] R2, R3, R4, R5 are each independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain thioalkoxy having 1 to 20 C atoms, branched-chain alkyl having 3 to 20 C atoms, branched-chain alkoxy having 3 to 20 C atoms, branched-chain thioalkoxy having 3 to 20 C atoms, cyclic alkyl having 3 to 20 C atoms, cyclic alkoxy having 3 to 20 C atoms, cyclic thioalkoxy having 3 to 20 C atoms, silyl, keto having 1 to 20 C atoms; , alkoxycarbonyl having 2 to 20 C atoms, aryloxycarbonyl having 7 to 20 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amine, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms, substituted or unsubstituted aryloxy groups having 5 to 20 ring atoms, substituted or unsubstituted heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these groups.

[0064] It can be understood that in the present invention, when V1 is a linking site, V1 is C.

[0065] Furthermore, L1 and L2 are independently selected from a single bond, a phenyl group or a carbazole group.

[0066] In another embodiment, L1 and L2 are both selected from single bonds.

[0067] In a specific example, M1 and M2 are independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted amine group.

[0068] In a specific example, M1 and M2 are independently selected from any of the following groups:

[0069]

[0070] in:

[0071] Each occurrence of X is independently selected from CR6 or N;

[0072] Each occurrence of Y is independently selected from NR7, CR8R9, SiR8R9, O, S, S=O or SO2;

[0073] R6, R7, R8, R9 are each independently selected from: -H, -D, straight-chain alkyl with 1 to 20 C atoms, straight-chain alkoxy with 1 to 20 C atoms, straight-chain thioalkoxy with 1 to 20 C atoms, branched-chain alkyl with 3 to 20 C atoms, branched-chain alkoxy with 3 to 20 C atoms, branched-chain thioalkoxy with 3 to 20 C atoms, cyclic alkyl with 3 to 20 C atoms, cyclic alkoxy with 3 to 20 C atoms, cyclic thioalkoxy with 3 to 20 C atoms, silyl, keto with 1 to 20 C atoms, 2 to 20 C atoms, 3 to 4 carbon atoms, 5 to 6 carbon atoms, 6 to 8 carbon atoms, 7 to 8 carbon atoms, 8 to 9 carbon atoms, 10 to 11 carbon atoms, 12 to 13 carbon atoms, 14 to 15 carbon atoms, 15 to 16 carbon atoms, 16 to 17 carbon atoms, 17 to 18 carbon atoms, 18 to 19 carbon atoms, 19 to 20 carbon atoms, 19 to 21 carbon atoms, 19 to 22 carbon atoms, 19 to 23 carbon atoms, 19 to 24 carbon atoms, 19 to 25 carbon atoms, 19 to 2 C atoms, alkoxycarbonyl, aryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, amine, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, substituted or unsubstituted aryloxy groups having 5 to 30 ring atoms, substituted or unsubstituted heteroaryloxy groups having 5 to 30 ring atoms, or combinations of these groups; R8 and R9 may or may not form a ring with each other;

[0074] Ar3 and Ar4 are independently selected from: substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms;

[0075] * indicates the attachment site.

[0076] It is understood that in the present invention, when X is a linking site, X is C.

[0077] In one embodiment, each occurrence of R6, R7, R8, and R9 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 10 C atoms, a branched-chain alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 3 to 10 C atoms, a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 20 ring atoms, or a combination of these groups.

[0078] In one embodiment, each occurrence of R6, R7, R8, and R9 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 4 C atoms, a branched-chain alkyl group having 3 to 4 C atoms, a cyclic alkyl group having 3 to 10 C atoms, a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 13 ring atoms, or a combination of these groups.

[0079] In a specific example, Ar3 and Ar4 are independently selected from any of the following groups:

[0080]

[0081] in:

[0082] Each occurrence of V2 is independently selected from CR 10 or N;

[0083] Y2 is selected from NR 11 , CR 12 R 13 、SiR 12 R 13 , O, S, S=O or SO2;

[0084] R 10 , R 11 , R 12 , R 13 Each occurrence is independently selected from: -H, -D, straight-chain alkyl with 1 to 20 C atoms, straight-chain alkoxy with 1 to 20 C atoms, straight-chain thioalkoxy with 1 to 20 C atoms, branched-chain alkyl with 3 to 20 C atoms, branched-chain alkoxy with 3 to 20 C atoms, branched-chain thioalkoxy with 3 to 20 C atoms, cyclic alkyl with 3 to 20 C atoms, cyclic alkoxy with 3 to 20 C atoms, cyclic thioalkoxy with 3 to 20 C atoms, silyl, keto with 1 to 20 C atoms, R is an alkyloxycarbonyl group having 6 to 20 ring atoms, an alkyloxycarbonyl group having 7 ... 12 and R 13 They may or may not form a ring with each other.

[0085] When V2 is a linking site, V2 is selected from C.

[0086] In one embodiment, R 10 , R 11 , R 12 , R 13Each occurrence is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 10 C atoms, branched-chain alkyl groups having 3 to 10 C atoms, cyclic alkyl groups having 3 to 10 C atoms, silyl groups, cyano groups, isocyano groups, hydroxyl groups, nitro groups, amine groups, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, substituted or unsubstituted heteroaromatic groups having 6 to 20 ring atoms, or combinations of these groups.

[0087] In one embodiment, R 10 , R 11 , R 12 , R 13 Each occurrence is independently selected from: -H, -D, straight-chain alkyl groups having 1 to 4 C atoms, branched-chain alkyl groups having 3 to 4 C atoms, cyclic alkyl groups having 3 to 10 C atoms, silyl groups, cyano groups, isocyano groups, hydroxyl groups, nitro groups, amine groups, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 6 to 13 ring atoms, or combinations of these groups.

[0088] Preferably, M1 and M2 are independently selected from substituted or unsubstituted amine groups, or substituted or unsubstituted heteroaromatic groups having 9 to 30 ring atoms. Heteroatoms have high electron density and high molar refractive index, which can increase the refractive index of the molecule and regulate the absorption range of the molecule, thereby increasing the absorption intensity in the ultraviolet range.

[0089] More preferably, the heteroaromatic group is selected from The molecular conjugated structure is large and planar, which can improve the thermal properties of the molecule, such as Tg and Td.

[0090] In a specific example, at least one of M1 and M2 is selected from Further, Selected from

[0091] In a specific example, the organic compound is selected from any one of the structures of formula (3-1) to (3-7):

[0092]

[0093] In a specific example, M1 and M2 are independently selected from any of the following groups:

[0094]

[0095] * indicates the attachment site.

[0096] In one embodiment, L1 and L2 in formula (3-1)-(3-7) are both selected from single bonds.

[0097] According to the organic compound of the present invention, the organic compound is selected from the following structures, but is not limited thereto:

[0098]

[0099]

[0100]

[0101]

[0102] In a specific example, the organic compound is a light extraction layer material.

[0103] The present invention further relates to a mixture, comprising at least one of the above organic compounds, and at least another organic functional material, wherein the at least another organic functional material can be selected from hole injection material (HIM), hole transport material (HTM), electron transport material (ETM), electron injection material (EIM), electron blocking material (EBM), hole blocking material (HBM), light emitting material (Emitter), host material (Host) and organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

[0104] The present invention also relates to a composition comprising at least one of the above-mentioned organic compounds or mixtures, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefin compounds, or borate or phosphate compounds, or a mixture of two or more solvents.

[0105] In a preferred embodiment, according to a composition of the present invention, at least one organic solvent is selected from aromatic or heteroaromatic based solvents.

[0106] Examples of aromatic or heteroaromatic solvents suitable for the present invention include, but are 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-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, ethyl 2-furoate, etc.

[0107] Examples of aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.

[0108] Examples of aromatic ether-based solvents suitable for the present invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethyl ethyl ether, 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, ethyl-2-naphthyl ether.

[0109] Suitable aliphatic ketone-based solvents for the present invention include, but are 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 aliphatic ethers, for example, amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0110] Examples of ester-based solvents suitable for the present invention include, but are not limited to, alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Methyl benzoate, octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate are particularly preferred.

[0111] The solvent may be used alone or as a mixture of two or more organic solvents.

[0112] In certain preferred embodiments, a composition according to the present invention is characterized in that it comprises at least one of the above organic compounds, or a mixture thereof and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene and / or mixtures thereof.

[0113] In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having a Hansen solubility parameter within the following ranges:

[0114] δd (dispersion force) is in the range of 17.0 to 23.2 MPa1 / 2, especially in the range of 18.5 to 21.0 MPa1 / 2;

[0115] δp (polar force) is in the range of 0.2 to 12.5 MPa1 / 2, especially in the range of 2.0 to 6.0 MPa1 / 2;

[0116] δh (hydrogen bonding force) is in the range of 0.9 to 14.2 MPa1 / 2, and particularly in the range of 2.0 to 6.0 MPa1 / 2.

[0117] According to the composition of the present invention, the organic solvent should be selected considering its boiling point parameter. In the present invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; more preferably ≥250°C; most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head. The organic solvent can be evaporated from the solvent system to form a film containing a functional material.

[0118] In a preferred embodiment, the composition according to the invention is a solution.

[0119] In another preferred embodiment, the composition according to the invention is a suspension.

[0120] The composition of the present invention may include 0.01 to 10 wt % of the compound or mixture according to the present invention, preferably 0.1 to 15 wt %, more preferably 0.2 to 5 wt %, and most preferably 0.25 to 3 wt %.

[0121] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0122] Among them, suitable printing or coating techniques include (but are not limited to): inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. The preferred ones are gravure printing, nozzle printing and inkjet printing. The solution or suspension may further include one or more components such as surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. Relevant printing technology and its related requirements for relevant solutions, such as solvents and concentrations, viscosity, etc.

[0123] The present invention further relates to a light extraction layer material selected from the above organic compounds or mixtures or compositions.

[0124] The present invention further relates to an application of the above organic compound, mixture or composition in an organic electroluminescent device.

[0125] The technical solution is as follows:

[0126] An organic electroluminescent device comprises two electrodes, one or more organic functional layers arranged between the two electrodes, and a light extraction layer arranged on the surface of one electrode and away from the organic functional layer, wherein the light extraction layer material comprises a compound as described in formula (1):

[0127]

[0128] in:

[0129] X1 and X2 are independently selected from O, S or NR1;

[0130] L1 and L2 are independently selected from: a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;

[0131] M1 and M2 are independently selected from: a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, and a substituted or unsubstituted amine group;

[0132] Each occurrence of R1 is independently selected from: -H, -D, straight-chain alkyl having 1 to 20 C atoms, branched alkyl having 3 to 20 C atoms, alkenyl having 2 to 20 C atoms, cyclic alkyl having 3 to 20 C atoms, substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms.

[0133] The further explanation of formula (1) is the same as described above.

[0134] In one embodiment, according to the organic electroluminescent device of the present invention, the light extraction layer is located on the cathode surface and away from the organic functional layer.

[0135] In some embodiments, according to the organic electroluminescent device of the present invention, the refractive index of the light extraction layer material at a wavelength of 630 nm is greater than 1.7; preferably, greater than 1.78; more preferably, greater than 1.83.

[0136] In some embodiments, according to the organic electroluminescent device of the present invention, the light extraction layer material needs a smaller extinction coefficient at a wavelength greater than 430nm, has a higher transmittance to visible light, and reduces the impact on the light extraction efficiency of the device. The extinction coefficient at a wavelength of 430nm is less than 0.1; preferably, less than 0.003; more preferably, less than 0.001.

[0137] In certain preferred embodiments, the organic electroluminescent device according to the present invention has a light extraction layer with a larger extinction coefficient in the wavelength range of ≤400nm; preferably, the extinction coefficient at a wavelength of 350nm is ≥0.3; preferably ≥0.5, more preferably ≥0.7, and most preferably ≥1.0.

[0138] In some embodiments, according to the organic electroluminescent device of the present invention, the thickness of the organic compound of the light extraction layer is generally 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 100nm, and most preferably 40nm to 90nm.

[0139] In some embodiments, according to the organic electroluminescent device of the present invention, the light extraction layer material needs a higher glass transition temperature to improve the thermal stability of the light extraction layer material. In some preferred embodiments, its glass transition temperature T g ≥100°C, in a preferred embodiment, T g ≥120℃, in a preferred embodiment, T g ≥140℃, in a more preferred embodiment, T g ≥160℃.

[0140] In one embodiment, the organic electroluminescent device according to the present invention includes one or more organic functional layers, and the organic functional layers are selected from one or more layers of electron injection layer, electron transport layer, hole injection layer, hole transport layer and light-emitting layer, and at least one light-emitting layer is included.

[0141] In certain preferred embodiments, in the organic electroluminescent device according to the present invention, the light-emitting material in the light-emitting layer is selected from a singlet light-emitting body, a triplet light-emitting body or a TADF material.

[0142] In some preferred embodiments, in the organic electroluminescent device according to the present invention, the organic functional layer is selected from a hole transport layer, a light emitting layer and an electron transport layer.

[0143] In some more preferred embodiments, in the organic electroluminescent device according to the present invention, the organic functional layer is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

[0144] For detailed description of singlet emitters, triplet emitters and TADF materials, please refer to WO2017092619A.

[0145] Further, according to the organic electroluminescent device of the present invention, the organic functional layer comprises a light-emitting layer; further, the light-emitting layer material is selected from triplet light-emitting materials.

[0146] In one embodiment, the triplet light-emitting material has the following general formula:

[0147]

[0148] Wherein: m is selected from 1 or 2 or 3;

[0149] Ring A is selected from substituted or unsubstituted N-containing heteroaromatic groups having 5 to 30 ring atoms;

[0150] Ring B is selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 30 ring atoms;

[0151] L is a monovalent anionic organic ligand.

[0152] In one embodiment, Ring A is selected from the following groups:

[0153]

[0154] Where: N is the connection site.

[0155] In one embodiment, Ring B is selected from the following groups:

[0156]

[0157] in:

[0158] Each occurrence of X3 is independently selected from CR 14 or N;

[0159] Each occurrence of Y3 is independently selected from CR 15 R 16 NR 17 、O、S、S=O、SO2、PR 17 , BR 17 、SiR 15 R 16 ;

[0160] R 14 -R 17 Multiple occurrences are independently selected from hydrogen, deuterium, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, cyano, nitro, CF3, OCF3, Cl, Br, F, substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, or combinations of these groups.

[0161] Furthermore, the triplet luminescent material is selected from the following general formula:

[0162]

[0163] Furthermore, the R 14Multiple occurrences are independently selected from hydrogen, deuterium, straight-chain alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, cyano, nitro, CF3, OCF3, Cl, Br, F, aromatic groups having 6 to 20 ring atoms, heteroaromatic groups having 5 to 20 ring atoms, or combinations of these groups;

[0164] When n occurs multiple times, it is independently selected from integers from 0 to 5.

[0165] The triplet luminescent material according to the present invention is selected from the following structures:

[0166]

[0167] The organic electronic device according to the present invention can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spin electronic devices, organic sensors and organic plasmon emission diodes, etc., and OLEDs are particularly preferred.

[0168] The cathode and anode in the device structure of the organic light emitting diode are described below.

[0169] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light-emitting layer. In 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 as the HIL or HTL or the electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include but are not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known and can be easily selected for use by a person skilled in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0170] The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore in the light-emitting layer or the n-type semiconductor material 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 OLEDs may be used as cathode materials for the device of the present invention. Examples of cathode materials include but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0171] The light extraction layer material needs to have a suitable energy level structure, with strong absorption in the region with a wavelength less than 400nm, and weak or close to zero absorption of visible light with a wavelength greater than 400nm, to prevent the internal materials of the device from being damaged by high-energy light in subsequent processes. At the same time, the light extraction layer material has a high refractive index, which can be used to beneficially guide the emission of visible light and improve the luminous efficiency of organic electronic light-emitting devices. When the reflectivity of the interface between the light extraction layer material and the adjacent electrode is large, the influence of light interference is large, so the refractive index of the light extraction layer material is preferably greater than the refractive index of the adjacent electrode.

[0172] In one embodiment, in the organic electroluminescent device, especially the organic light emitting diode, according to the present invention, the light extraction layer is located on the cathode surface.

[0173] In some more preferred embodiments, according to the organic electroluminescent device of the present invention, the thickness of the organic compound of the light extraction layer is generally 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 100nm, and most preferably 40nm to 90nm.

[0174] The present invention also relates to the application of the electroluminescent device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors and the like.

[0175] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific embodiments

[0177] The organic compound and the preparation method of the present invention are further described in detail below in conjunction with specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.

[0178] Example 1

[0179] This embodiment provides an organic compound C26, and the specific synthesis route is as follows:

[0180]

[0181] Dissolve carbazole (3.34 g, 20 mmol) in anhydrous DMF, cool to 0 degrees, add sodium hydride and continue stirring for half an hour, add intermediate Z1 (3.74 g, 20 mmol), naturally heat up and track by TLC. After the reaction is complete, add deionized water and extract with ethyl acetate, wash the organic layer three times with water, and concentrate it on a silica gel column to obtain 5.4 g of intermediate Z2, with a yield of 85%.

[0182] The intermediate Z2 (4.77 g, 15 mmol) was dissolved in anhydrous tetrahydrofuran, potassium acetate (3 g, 30 mmol), biboronic acid pinacol ester (4.06 g, 16 mmol) and dichlorobistriphenylphosphine palladium (0.32 g, 0.45 mmol) were added, nitrogen was replaced, and the temperature was raised to reflux. The reaction was stirred for 12 hours, and the system was cooled, and water was added to separate the organic phase, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain a total of 4.8 g of the intermediate Z3, with a yield of 78%.

[0183] Dissolve Z1 (1.87 g, 10 mmol) and Z3 (4.1 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually heat to 80 ° C, stir and react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.13 g of product Z4 with a yield of 72%.

[0184] Compound Z4 (2.61 g, 6 mmol) and Z5 (1.72 g, 6 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.67 g, 7 mmol) and tris dibenzylideneacetone dipalladium (0.16 g, 0.18 mmol) were added, and nitrogen was replaced three times, and tri-tert-butylphosphine (0.18 mmol) was added, and the temperature was gradually raised to 80°C, and the reaction was stirred for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain 3.33 g of product C26, with a yield of 81%; MS: 685 [M + ].

[0185] Example 2

[0186] This embodiment provides an organic compound C1, and the specific synthesis route is as follows:

[0187]

[0188] Compound Z4 (4.35 g, 10 mmol) and carbazole (1.84 g, 11 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15 g, 12 mmol) and tris dibenzylideneacetone dipalladium (0.27 g, 0.3 mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3 mmol) was added, the temperature was gradually raised to 80°C, stirred for reaction for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain 3.9 g of product C1, with a yield of 69%; MS: 566 [M + ].

[0189] Example 3

[0190] This embodiment provides an organic compound C3, and the specific synthesis route is as follows:

[0191]

[0192] The intermediate Z4 (4.35 g, 10 mmol) was dissolved in anhydrous tetrahydrofuran, potassium acetate (1.96 g, 20 mmol), biboronic acid pinacol ester (3.05 g, 12 mmol) and dichlorobistriphenylphosphine palladium (0.27 g, 0.3 mmol) were added, and the temperature was raised to reflux. The reaction was stirred for 12 hours, and the system was cooled, and water was added to separate the organic phase, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain a total of 3.48 g of intermediate Z6 with a yield of 66%.

[0193] Dissolve Z6 (3.16 g, 6 mmol) and Z7 (0.92 g, 6 mmol) in anhydrous toluene and methanol, add potassium carbonate (1.66 g, 12 mmol) and tetrakistriphenylphosphine palladium (0.2 g, 0.18 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 2.27 g of product C3, with a yield of 73%. MS: 518 [M + ].

[0194] Example 4

[0195] This embodiment provides an organic compound C7, and the specific synthesis route is as follows:

[0196]

[0197] Dissolve Z1 (5.61 g, 30 mmol) and 9-phenylcarbazole-3-boric acid (8.61 g, 30 mmol) in anhydrous toluene and methanol, add potassium carbonate (12.42 g, 90 mmol) and tetrakistriphenylphosphine palladium (1.04 g, 0.9 mmol), replace nitrogen three times, gradually heat up to 80 ° C, stir and react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 9.1 g of product Z8 with a yield of 77%.

[0198] The intermediate Z8 (7.88 g, 20 mmol) was dissolved in anhydrous tetrahydrofuran, potassium acetate (3.92 g, 40 mmol), biboronic acid pinacol ester (5.6 g, 22 mmol) and dichlorobistriphenylphosphine palladium (0.42 g, 0.6 mmol) were added, and the temperature was raised to reflux. The reaction was stirred for 12 hours, and the system was cooled, and water was added to separate the organic phase, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain a total of 8.16 g of the intermediate Z9, with a yield of 84%.

[0199] Dissolve Z9 (7.29 g, 15 mmol) and Z1 (2.8 g, 15 mmol) in anhydrous toluene and methanol, add potassium carbonate (4.14 g, 30 mmol) and tetrakistriphenylphosphine palladium (0.52 g, 0.45 mmol), replace nitrogen three times, gradually heat to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 4.98 g of product Z10, with a yield of 65%.

[0200] Dissolve Z10 (4.1 g, 8 mmol) and 9-phenylcarbazole-3-boronic acid (2.3 g, 8 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.21 g, 16 mmol) and tetrakistriphenylphosphine palladium (0.28 g, 0.24 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.5 g of product C7, with a yield of 61%. MS: 718 [M + ].

[0201] Example 5

[0202] This example provides an organic compound C101, and the specific synthesis route is as follows:

[0203]

[0204] Dissolve Z11 (5.61 g, 30 mmol) and dibenzothiophene boronic acid (6.84 g, 30 mmol) in anhydrous toluene and methanol, add 8.28 g, 60 mmol) and tetrakistriphenylphosphine palladium (1.04 g, 0.9 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 8.04 g of product Z12 with a yield of 80%.

[0205] The intermediate Z12 (6.7 g, 20 mmol) was dissolved in anhydrous tetrahydrofuran, potassium acetate (3.92 g, 40 mmol), biboronic acid pinacol ester (5.6 g, 22 mmol) and dichlorobistriphenylphosphine palladium (0.42 g, 0.6 mmol) were added, and the temperature was raised to reflux. The reaction was stirred for 12 hours, and the system was cooled, and water was added to separate the organic phase, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain a total of 5.29 g of the intermediate Z13, with a yield of 62%.

[0206] Dissolve Z13 (4.27 g, 10 mmol) and Z11 (1.87 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually heat up to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.25 g of product Z14, with a yield of 72%.

[0207] Compound Z14 (3.16 g, 7 mmol) and diphenylamine (1.18 g, 7 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.77 g, 8 mmol) and tris dibenzylideneacetone dipalladium (0.19 g, 0.21 mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.21 mmol) was added, the temperature was gradually raised to 80°C, stirred for reaction for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain 3.56 g of product C101, with a yield of 87%; MS: 585 [M + ].

[0208] Example 6

[0209] This embodiment provides an organic compound C49, and the specific synthesis route is as follows:

[0210]

[0211] Dissolve Z15 (4.04 g, 20 mmol) and dibenzothiophene boronic acid (4.56 g, 20 mmol) in anhydrous toluene and methanol, add potassium carbonate (5.52 g, 40 mmol) and tetrakistriphenylphosphine palladium (0.69 g, 0.6 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 5.46 g of product Z16 with a yield of 78%.

[0212] The intermediate Z16 (4.9 g, 14 mmol) was dissolved in anhydrous tetrahydrofuran, potassium acetate (2.75 g, 28 mmol), biboronic acid pinacol ester (4.06 g, 16 mmol) and dichlorobistriphenylphosphine palladium (0.29 g, 0.42 mmol) were added, and the temperature was raised to reflux. The reaction was stirred for 12 hours, and the system was cooled, and water was added to separate the organic phase, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain a total of 5.15 g of intermediate Z17 with a yield of 83%.

[0213] Dissolve Z17 (4.43 g, 10 mmol) and Z15 (2.03 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually heat to 80 ° C, stir and react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.63 g of product Z18 with a yield of 75%.

[0214] Dissolve Z18 (3.39 g, 7 mmol) and dibenzothiophene boronic acid (1.6 g, 7 mmol) in anhydrous toluene and methanol, add potassium carbonate (1.93 g, 14 mmol) and tetrakistriphenylphosphine palladium (0.24 g, 0.21 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 2.74 g of product C49, with a yield of 62%. MS: 632 [M + ].

[0215] Example 7

[0216] This embodiment provides an organic compound C50, and the specific synthesis route is as follows:

[0217]

[0218] Dissolve Z15 (5.07 g, 25 mmol) and 9-phenanthrene boronic acid (5.55 g, 25 mmol) in anhydrous toluene and methanol, add potassium carbonate (6.9 g, 50 mmol) and tetrakistriphenylphosphine palladium (0.87 g, 0.75 mmol), replace nitrogen three times, gradually heat to 80 ° C, stir and react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 6.21 g product Z19, with a yield of 72%;

[0219] Dissolve the intermediate Z19 (5.86 g, 17 mmol) in anhydrous tetrahydrofuran, add potassium acetate (3.33 g, 34 mmol), biboronic acid pinacol ester (4.83 g, 19 mmol) and dichlorobistriphenylphosphine palladium (0.36 g, 0.51 mmol), and heat to reflux. Stir the reaction for 12 hours, wait for the system to cool, add water to separate the organic phase, extract with ethyl acetate three times, concentrate under reduced pressure, and pass through a silica gel column to obtain a total of 4.53 g of intermediate Z20, with a yield of 61%;

[0220] Dissolve Z20 (4.37 g, 10 mmol) and Z15 (2.03 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually raise the temperature to 80 ° C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.06 g of product Z21, with a yield of 64%;

[0221] Dissolve Z21 (2.87 g, 6 mmol) and 9-phenanthrene boronic acid (1.33 g, 6 mmol) in anhydrous toluene and methanol, add potassium carbonate (1.66 g, 12 mmol) and tetrakistriphenylphosphine palladium (0.21 g, 0.18 mmol), replace nitrogen three times, gradually raise the temperature to 80°C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 2.16 g of product C50, with a yield of 58%, MS: 620 [M + ].

[0222] Example 8

[0223] This embodiment provides an organic compound C56, and the specific synthesis route is as follows:

[0224]

[0225] Compound Z15 (5.07 g, 25 mmol) and carbazole (6.08 g, 25 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.88 g, 30 mmol) and tris dibenzylideneacetone dipalladium (0.69 g, 0.75 mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.75 mmol) was added, the temperature was gradually raised to 80°C, stirred for reaction for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and filtered through silica gel to obtain 8.4 g of product Z22, with a yield of 82%;

[0226] Dissolve the intermediate Z22 (8.2 g, 20 mmol) in anhydrous tetrahydrofuran, add potassium acetate (3.92 g, 40 mmol), biboronic acid pinacol ester (5.6 g, 22 mmol) and dichlorobistriphenylphosphine palladium (0.42 g, 0.6 mmol), and heat to reflux. Stir the reaction for 12 hours, wait for the system to cool, add water to separate the organic phase, extract with ethyl acetate three times, concentrate under reduced pressure, and pass through a silica gel column to obtain 5.82 g of the intermediate Z23, with a yield of 58%;

[0227] Dissolve Z23 (5.02 g, 10 mmol) and Z15 (2.03 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually raise the temperature to 80 ° C, and stir to react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 3.31 g product Z24, with a yield of 61%;

[0228] Compound Z24 (3.26 g, 6 mmol) and diphenylamine (1.01 g, 6 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.67 g, 7 mmol) and tris dibenzylideneacetone dipalladium (0.16 g, 0.18 mmol) were added, and nitrogen was replaced three times, and tri-tert-butylphosphine (0.18 mmol) was added, and the temperature was gradually raised to 80°C, and the reaction was stirred for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain 2.11 g of product C56, with a yield of 52%, MS: 676 [M + ].

[0229] Example 9

[0230] This embodiment provides an organic compound C82, and the specific synthesis route is as follows:

[0231]

[0232] Dissolve compound Z11 (5.61 g, 30 mmol) and carbazole (6.51 g, 30 mmol) in anhydrous toluene, add sodium tert-butoxide (3.46 g, 36 mmol) and tris dibenzylideneacetone dipalladium (0.82 g, 0.9 mmol), replace nitrogen three times, add tri-tert-butylphosphine (0.9 mmol), gradually raise the temperature to 80°C, stir and react for 12 hours, and remove the heat source. After the system is cooled, add deionized water, separate the organic layer, extract it with ethyl acetate three times, concentrate it under reduced pressure, and pass it through silica gel to obtain 8.28 g of product Z25, with a yield of 75%;

[0233] Dissolve the intermediate Z25 (7.36 g, 20 mmol) in anhydrous tetrahydrofuran, add potassium acetate (3.92 g, 40 mmol), biboronic acid pinacol ester (5.6 g, 22 mmol) and dichlorobistriphenylphosphine palladium (0.42 g, 0.6 mmol), and heat to reflux. Stir the reaction for 12 hours, wait for the system to cool, add water to separate the organic phase, extract with ethyl acetate three times, concentrate under reduced pressure, and pass through a silica gel column to obtain a total of 4.97 g of intermediate Z26, with a yield of 54%;

[0234] Dissolve Z26 (4.6 g, 10 mmol) and Z11 (1.87 g, 10 mmol) in anhydrous toluene and methanol, add potassium carbonate (2.76 g, 20 mmol) and tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), replace nitrogen three times, gradually heat to 80 ° C, stir and react. When the TLC spot plate reactant disappears, remove the heat source. After the system is cooled, add water, separate the organic layer, and extract it with ethyl acetate three times, concentrate under reduced pressure, and pass through silica gel to obtain 2.81 g product Z27, with a yield of 58%;

[0235] Compound Z27 (2.42 g, 5 mmol) and carbazole (1.09 g, 5 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.67 g, 7 mmol) and tris dibenzylideneacetone dipalladium (0.16 g, 0.18 mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.18 mmol) was added, the temperature was gradually raised to 80°C, stirred for reaction for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, and extracted with ethyl acetate three times, concentrated under reduced pressure, and passed through a silica gel column to obtain 1.53 g of product C82, with a yield of 46%, MS: 666 [M + ].

[0236] Extinction coefficient and refractive index test

[0237] The compound was deposited on single crystal silicon by vacuum evaporation to form a 50nm thin film. The single crystal silicon was placed on the sample stage of the ellipsometer (ES-01), with an incident angle of 70°. The test was in the atmospheric environment. The extinction coefficient (k) and refractive index (n) test results of the compound were obtained by fitting the ellipsometer. The results are shown in Table 1:

[0238] Table 1

[0239] Compound Extinction coefficient@430nm Refractive index@630nm C26 0.08 1.90 C1 0 1.85 C3 0 1.88 C7 0 1.88 C101 0.02 1.89 C49 0 1.86 C50 0 1.82 C56 0.05 1.90 C82 0 1.87 CBP 0 1.74

[0240] The compound of the present invention has weak absorption in the visible light band and high absorption in the ultraviolet band, and can resist the damage of external high-energy light to the inside of the device. The higher refractive index can ensure better light extraction effect.

[0241] Preparation and characterization of OLED devices

[0242] The following is a detailed description of the preparation process of the OLED device using the above-mentioned embodiment. The structure of the OLED device is: ITO / Ag / ITO (anode) / HATCN / SFNFB / m-CP:Ir(p-ppy)3 / NaTzF2 / LiF / Mg:Ag / light extraction layer. Figure 1 The specific preparation steps are as follows:

[0243] The ITO conductive glass anode layer was cleaned, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, and then treated in a plasma cleaner for 5 minutes to improve the electrode work function. On the ITO anode layer, the hole injection layer material HATCN was evaporated by vacuum evaporation with a thickness of 5nm and an evaporation rate of On the hole injection layer, the hole transport material SFNFB is vacuum deposited with a thickness of 80nm. On the hole transport layer, the light-emitting layer is deposited, with m-CP as the main material and Ir(p-ppy)3 as the doping material. The mass ratio of Ir(p-ppy)3 and m-CP is 1:9, and the thickness is 30nm. On the light-emitting layer, the electron transport material NaTzF2 is vacuum deposited with a thickness of 30nm. On the electron transport layer, the electron injection layer LiF is vacuum deposited with a thickness of 1nm. This layer is the electron injection layer. On the electron injection layer, the cathode Mg:Ag layer is vacuum deposited with a Mg:Ag doping ratio of 9:1 and a thickness of 15nm. On the cathode layer, the light extraction layer compound C26 is vacuum deposited with a thickness of 60nm.

[0244] Device Example 2: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to C1.

[0245] Device Example 3: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to C3.

[0246] Device Example 4: The compound C26 in the light extraction layer of the organic electroluminescent device is changed to C7.

[0247] Device Example 5: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to C101.

[0248] Device Example 6: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to C49.

[0249] Device Example 7: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to C50.

[0250] Device Example 8: The compound C26 in the light extraction layer of the organic electroluminescent device is changed to C56.

[0251] Device Example 9: The compound C26 in the light extraction layer of the organic electroluminescent device is changed to C82.

[0252] Device Comparative Example 1: The compound C26 of the light extraction layer of the organic electroluminescent device is changed to CBP.

[0253] Device Comparative Example 2: The compound C26 of the light extraction layer of the organic electroluminescent device was changed to Ref.-1.

[0254] The structures of the compounds involved in the device are as follows:

[0255]

[0256] Table 2

[0257] serial number Light extraction layer compound Luminous efficiency Device Example 1 C26 1.19 Device Example 2 C1 1.12 Device Example 3 C3 1.14 Device Example 4 C7 1.14 Device Example 5 C101 1.16 Device Example 6 C49 1.13 Device Example 7 C50 1.07 Device Example 8 C56 1.18 Device Example 9 C82 1.13 Comparative Example 1 CBP 1 Comparative Example 2 Ref.-1 1.03

[0258] The luminous efficiency in Table 2 is the current density of 10mA / cm 2 It can be seen from Table 2 that compared with the comparative example, the compound of the present invention as a light extraction layer can effectively improve the luminous efficiency of the organic electroluminescent device.

[0259] The above-described embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in detail, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the contents of the attached claims, and the description can be used to interpret the contents of the claims.

Claims

1. An organic compound, characterized in that Its structure is shown in the general formula (1): in: X1 and X2 are independently selected from O or S; L1 and L2 are single bonds; M1 and M2 are independently selected from any of the following groups: Each occurrence of X is independently selected from CR6; Each occurrence of Y is independently selected from NR7, O or S; R6 and R7, at each occurrence, are independently selected from: -H, -D or an aromatic group having 6 to 10 ring atoms; Ar3 and Ar4 are independently selected from any of the following groups: Each occurrence of V2 is independently selected from CR 10 or N; Y2 is selected from O or S; R 10 Each occurrence is independently selected from: -H, -D or an aromatic group having 6 to 10 ring atoms; * indicates the attachment site.

2. The organic compound according to claim 1, characterized in that The structure of the organic compound is shown in general formula (2-1) or (2-2):

3. The organic compound according to claim 1, characterized in that M1 and M2 are independently selected from any of the following groups: * indicates the attachment site.

4. The organic compound according to claim 1, characterized in that The organic compound is selected from any one of the structures of formula (3-1)-(3-2) and formula (3-4)-(3-7):

5. The organic compound according to claim 1, characterized in that The organic compound is selected from any of the following structures:

6. A mixture, characterized in that The mixture comprises the organic compound according to any one of claims 1 to 5, 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 or host materials.

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

8. A light extraction layer material, characterized in that: The light extraction layer material comprises the organic compound according to any one of claims 1 to 5, the mixture according to claim 6, or is prepared from the composition according to claim 7.

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

10. The organic electronic device according to claim 9 comprises two electrodes, one or more organic functional layers arranged between the two electrodes, and a light extraction layer arranged on the surface of one electrode and away from the organic functional layer, wherein the light extraction layer material comprises the organic compound according to any one of claims 1 to 5, the mixture according to claim 6, or is prepared from the composition according to claim 7.

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