Organic compounds, mixtures, compositions and organic electronic devices

Abstract

The present invention relates to the field of electroluminescence, and in particular to an organic compound, a mixture, a composition and an organic electronic device, wherein the organic compound has a structure as shown in general formula (1). The organic compound of the present invention is a new type of material, which can improve the stability and life of the device as an electron blocking material.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to organic compounds, mixtures, compositions and organic electronic devices. Background Art

[0002] Organic optoelectronic materials are diverse in structure, have relatively low manufacturing costs, and have excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) are used in optoelectronic devices, such as flat-panel displays and lighting, and have advantages such as wide viewing angle, fast response time, low operating voltage, and thin panel thickness, and therefore have broad development potential.

[0003] Organic electroluminescence refers to the phenomenon of converting organic substances into light energy under the excitation of electrical energy. The structure of an organic electroluminescent element that utilizes the organic electroluminescence phenomenon usually has a positive electrode and a negative electrode and an organic functional layer contained therein. In order to improve the efficiency and life of the organic electroluminescent element, the organic functional layer generally has a multilayer structure, and each layer contains organic substances with different functions. Specifically, the functional layer may include a hole injection layer, a hole transport layer, a luminescent auxiliary layer, a luminescent layer, an electron transport layer, an electron injection layer, and the like. In this organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, and electrons are injected from the negative electrode into the organic functional layer. When the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to the ground state. This organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, and high contrast.

[0004] In order to improve the performance of organic electroluminescent devices, in addition to developing high-performance luminescent materials, the development of luminescent auxiliary materials is also very important. At present, although a large number of luminescent auxiliary materials have been developed, the corresponding devices still have many problems such as unbalanced carrier transmission and insufficient device life. How to design new materials with better performance to achieve the effect of adjusting transmission balance and improving device efficiency and life has always been a problem that technicians in this field need to solve. Summary of the invention

[0005] Based on this, the object of the present invention is to provide an organic compound, a mixture, a composition and an organic electronic device to improve the efficiency and life of the organic electronic device.

[0006] The technical solution of the present invention is as follows:

[0007] An organic compound having a structure as shown in general formula (1):

[0008]

[0009] Wherein: Ar1 is selected from 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;

[0010] Ar2-Ar6 are each independently selected from an alkyl 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 combination of these groups;

[0011] L1 is selected from 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;

[0012] L2 is selected from an alkyl 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;

[0013] R1 is independently selected at each occurrence from -H, -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20 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 combination of these groups;

[0014] Adjacent R1s may or may not form a ring with each other;

[0015] a, b are independently selected from 0, 1 or 2; c is selected from 0, 1, 2, 3 or 4; n, m are selected from 0 or 1, and n+m is greater than or equal to 1.

[0016] The present invention further relates to a mixture, which comprises the above-mentioned 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 and organic dyes.

[0017] The present invention further relates to a composition comprising the above organic compound or the above mixture and at least one organic solvent.

[0018] The present invention further relates to an organic electronic device, comprising a first electrode, a second electrode and one or more organic functional layers located between the first electrode and the second electrode, at least one of the organic functional layers comprising the above-mentioned organic compound or the above-mentioned mixture or prepared from the above-mentioned composition.

[0019] Beneficial effects:

[0020] The organic compound described in the present invention is a new type of material, in the structure of which a non-conjugated group - cyclopentane group is fused. With the cooperation of amino group, it can better regulate the transmission of holes and the charge transmission balance in the device. As an electron blocking layer, it can improve the stability and life of the device. DETAILED DESCRIPTION

[0021] The present invention provides an organic compound, a mixture, a composition and an organic electronic device. In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

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

[0023] In the present invention, 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.

[0024] 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 atoms, cyano groups, isocyano groups, nitro groups or halogens, C 1-30 Alkyl, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silanyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups can also be further substituted by substituents acceptable in the art; it can be understood that R' and R" in -NR'R" are independently selected from but not limited to: H, deuterium atom, cyano, isocyano, nitro or halogen, C 1-10 Alkyl, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms.

[0025] 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.

[0026] "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.

[0027] "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, imidazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyridinyl, oxazine, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzothiophenyl, benzofuranyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolyl, isoquinolyl, o-naphthyl, quinoxalinyl, phenanthridinyl, primary pyridyl, quinazolinyl, quinazolinone, dibenzothiophenyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0028] 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 1-9The term "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-butyl, 2-ethyl ... 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.

[0029] 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.

[0030] "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.

[0031] In the present invention, "*" connected to a single bond indicates a connection or fusion site.

[0032] 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 the linking site.

[0033] 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 used as the fusion site.

[0034] In the present invention, when a 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.

[0035] 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 R is connected to any substitutable position of the benzene ring; express Fused with any adjacent C atom on benzene.

[0036] The technical solution of the present invention is as follows:

[0037] An organic compound having a structure as shown in general formula (1):

[0038]

[0039] Wherein: Ar1 is selected from 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;

[0040] Ar2-Ar6 are each independently selected from an alkyl 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 combination of these groups;

[0041] L1 is selected from 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;

[0042] L2 is selected from an alkyl 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;

[0043] R1 is independently selected at each occurrence from -H, -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20 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 combination of these groups;

[0044] Adjacent R1s may or may not form a ring with each other;

[0045] a, b are independently selected from 0, 1 or 2; c is selected from 0, 1, 2, 3 or 4; n, m are selected from 0 or 1, and n+m is greater than or equal to 1.

[0046] In one embodiment, b is selected from 1 or 2.

[0047] In one embodiment, m is selected from 1, and b is selected from 1 or 2.

[0048] In one embodiment, Ar1 is selected from 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; further, Ar1 is selected from 0 A substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms; wherein: R 0 is selected from -D, or a straight-chain alkyl group having 1 to 10 C atoms, or a branched-chain alkyl group having 3 to 10 C atoms, or a cyclic alkyl group having 3 to 10 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, -CF3, -Cl, -Br, -F, -I, or an aromatic group having 6 to 10 ring atoms, or a heteroaromatic group having 6 to 10 ring atoms.

[0049] In one embodiment, Ar1 is selected from 0 A substituted or unsubstituted aromatic group having 6 to 18 ring atoms, or R 0 a substituted or unsubstituted heteroaromatic group having 6 to 18 ring atoms;

[0050] Further, Ar1 is selected from one of the following groups:

[0051]

[0052] Wherein: Y represents a member selected from NR2, CR3R4, O, S, SiR3R4 or PR2;

[0053] R2-R4 are each independently selected from -H, -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20 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 combination of these groups;

[0054] R3 and R4 may or may not form a ring with each other.

[0055] In some embodiments, the Ar1 is selected from one of the following groups:

[0056]

[0057] Wherein: * indicates the fusion site.

[0058] The above Ar1 group can be further R 0 replace.

[0059] In one embodiment, R2-R4 are independently selected from -H, -D, or a straight-chain alkyl group having 1 to 10 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 10 C atoms, or a cyclic alkoxy group having 3 to 10 C atoms, or a keto group having 1 to 10 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 10 C atoms, or R 0 A substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.

[0060] In some embodiments, the organic compound has a structure as shown in any one of the general formulas (1-1) to (1-7):

[0061]

[0062] In some embodiments, L1 is selected from 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.

[0063] Further, L1 is selected from R 0 A substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, wherein: R 0 The meaning is the same as above.

[0064] Further, L1 is selected from R 0 A substituted or unsubstituted aromatic group having 6 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 6 ring atoms, wherein: R 0 The meaning is the same as above.

[0065] In some embodiments, a is 0.

[0066] In one embodiment, m is selected from 1, b is selected from 1 or 2, and L2 is selected from 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. 0 A substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, wherein: R 0 The meaning is the same as above. Furthermore, L2 is independently selected from one of the following groups:

[0067]

[0068] Wherein, d represents an integer of 0-4, and * represents a connection site.

[0069] In one embodiment, m is selected from 0, b is selected from 1 or 2, L2 is selected from an alkyl 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; further, L2 is selected from an alkyl group having 1 to 10 C atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms. 0 A substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or R 0 A substituted or unsubstituted heteroaromatic group having 6 to 20 ring atoms. Furthermore, L2 is independently selected from one of the following groups:

[0070]

[0071] Wherein, e represents an integer from 0 to 5, and * represents a connection site.

[0072] In one embodiment, the organic compound has a structure as shown in any one of the general formulas (2-1) to (2-15):

[0073]

[0074]

[0075] In some embodiments, Ar2 is selected from one or a combination of the following groups:

[0076]

[0077] in:

[0078] X, at each occurrence, is independently selected from CR5 or N;

[0079] Each occurrence of Z is independently selected from NR6, CR7R8, SiR7R8, O, S or PR6;

[0080] R5-R8, at each occurrence, are independently selected from -H, -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20 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 combination of these groups;

[0081] * indicates the attachment site.

[0082] It should be noted that when X is a linking site, X is selected from C.

[0083] Further, Ar2 is selected from 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, or phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, perylene, acenaphthene, thienyl, furanyl, pyrrolyl, imidazolyl, triazolyl, imidazolyl, diazolyl, triazolyl, pyridyl, bipyridine , 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 101, 102, 114, 115, 116, 117, 118, 123, 119, 124, 125

[0084] The Ar3-Ar6 are independently selected from one or a combination of the following groups:

[0085]

[0086] Wherein: X and Z have the same meanings as above.

[0087] Preferably, Ar3-Ar6 are independently selected from one or a combination of the following groups:

[0088]

[0089] Among them: the above groups are unsubstituted or replaced by R 0 replace.

[0090] Preferably, Where Ar3 is selected from

[0091] Preferably, Ar5 is selected from

[0092] In some of these embodiments, and Each is independently selected from one of the following structures:

[0093]

[0094]

[0095] Among them: the above groups are unsubstituted or replaced by R 0 Substitution; * indicates the attachment site.

[0096] The compounds according to the present invention are preferably selected from but not limited to the following structures, which may be arbitrarily substituted:

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] The organic compound according to the present invention can be used as a functional material in the functional layer of an electronic device. The organic functional layer includes, but is not limited to, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron injection layer (EIL), an electron blocking layer (EBL), a hole blocking layer (HBL), and an emitting layer (EML).

[0106] In one embodiment, the organic compound according to the present invention is used in a hole transport layer or an electron blocking layer. Furthermore, the organic compound according to the present invention is used in a hole transport layer or an electron blocking layer of a red light emitting organic electronic device.

[0107] The present invention further relates to a mixture, comprising at least one organic compound as described above, and at least one organic functional material, wherein the at least one 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), luminescent 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.

[0108] In one embodiment, the organic functional material is selected from electron transport materials and is used as a co-host in electronic devices.

[0109] The present invention also relates to a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent. The at least one organic solvent is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or boric acid esters or phosphate esters, or a mixture of two or more solvents.

[0110] In a preferred embodiment, a composition according to the present invention is characterized in that the at least one organic solvent is selected from aromatic or heteroaromatic based solvents.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] Examples of aliphatic ketone-based solvents suitable 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.

[0115] 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.

[0116] The solvent may be used alone or as a mixture of two or more organic solvents.

[0117] In certain preferred embodiments, a composition according to the present invention is characterized in that it comprises at least one organic compound or mixture as described above 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.

[0118] In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having a Hansen solubility parameter within the following ranges:

[0119] δd (dispersion force) at 17.0MPa 1 / 2 ~23.2MPa 1 / 2 range, especially at 18.5MPa 1 / 2 ~21.0MPa 1 / 2 scope;

[0120] δp (polar force) at 0.2MPa 1 / 2 ~12.5MPa 1 / 2 range, especially at 2.0MPa 1 / 2 ~6.0MPa 1 / 2 scope;

[0121] δh (hydrogen bond force) at 0.9MPa 1 / 2 ~14.2MPa 1 / 2 range, especially at 2.0MPa 1 / 2 ~6.0MPa 1 / 2 range.

[0122] 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.

[0123] In a preferred embodiment, the composition according to the invention is a solution.

[0124] In another preferred embodiment, the composition according to the invention is a suspension.

[0125] The composition in the embodiment of the present invention may include 0.01wt% to 10wt% of the compound or mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 5wt%, and most preferably 0.25wt% to 3wt%.

[0126] 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.

[0127] 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.

[0128] The present invention also provides an application of the organic compound, mixture or composition as described above in the preparation of an organic electronic device. The technical solution is as follows:

[0129] An organic electronic device comprises a first electrode, a second electrode and one or more organic functional layers located between the first electrode and the second electrode, wherein at least one of the organic functional layers comprises the organic compound, mixture or is prepared from the above-mentioned composition. Further, the organic electronic device comprises a cathode, an anode and one or more organic functional layers located at the cathode and the anode.

[0130] The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spin electronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., and organic electroluminescent devices such as OLED, OLEEC, and organic light emitting field effect transistors are particularly preferred.

[0131] In one embodiment, the organic functional layer comprises an electron blocking layer, and the electron blocking layer comprises the organic compound or mixture as described above or is prepared from the above composition. The specific definition of the organic compound is as described above.

[0132] The organic functional layer according to the present invention can be selected from a hole injection layer (HIL), a hole transport layer (HTL), an emitting layer (EML), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0133] In one embodiment, the organic electronic device comprises a cathode, an anode, a hole transport layer, a hole injection layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer.

[0134] The light emitting device described above, especially OLED, comprises a substrate, an anode, at least one electron blocking layer and a light emitting layer, and a cathode.

[0135] The substrate can be opaque or transparent. 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 be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best that the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics, and its glass transition temperature Tg is above 150°C, preferably above 200°C, more preferably above 250°C, and preferably above 300°C. Examples of suitable flexible substrates include poly (ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0136] The anode may include 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 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), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0137] The cathode may include 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.

[0138] The present invention also relates to the use of the electroluminescent device according to the present invention in the preparation of various electronic devices, including, but not limited to: display devices, lighting devices, light sources, sensors, etc.

[0139] 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

[0141] 1. Synthesis of compounds

[0142] Example 1: Synthesis of compound (M1):

[0143]

[0144] 1) Synthesis of intermediate M1-3: Under nitrogen environment, (19.8 g, 100 mmol) of compound M1-1, (28.3 g, 100 mmol) of compound M1-2, (3.31 g, 3 mmol) of tetrakistriphenylphosphine palladium, (27.6 g, 200 mmol) of potassium carbonate in 50 mL of aqueous solution and 200 mL of toluene were added to a 500 mL three-necked flask, heated and stirred to 60 ° C for 12 hours, the reaction was terminated, cooled to room temperature, the reaction solution was filtered, most of the filtrate was evaporated by rotary evaporation, dissolved in dichloromethane and washed three times, the organic liquid was collected and mixed with silica gel for column chromatography purification, the yield was 75%.

[0145] 2) Synthesis of intermediate M1-5: Under nitrogen environment, (23.4 g, 60 mmol) of compound M1-3 and 150 mL of anhydrous tetrahydrofuran solvent were added to a 500 mL two-necked flask, stirred to dissolve, cooled to -78 ° C, 60 mmol of n-butyl lithium was slowly added dropwise, the temperature was maintained, and the reaction was continued with stirring for 2 hours. The reaction solution was transferred to 100 mL of anhydrous tetrahydrofuran solution containing (16.7 g, 60 mmol) of compound M1-4, and the reaction was stirred at room temperature for 4 hours. Water was added to quench, and most of the solvent was evaporated from the reaction solution by rotary evaporation, and the solution was washed 3 times with dichloromethane and water. The organic phase was collected and directly used as the raw material for the next step after spin drying.

[0146] 3) Synthesis of intermediate M1-6: Add compound M1-5 obtained in the previous step, 80 mL of acetic acid and 15 mL of hydrobromic acid into a 250 mL two-necked flask, heat to 100°C and stir for 12 hours, terminate the reaction, add the reaction solution into 300 mL of water, filter with suction, and recrystallize the residue with ethyl acetate / ethanol mixed solution. The total yield of the two steps is 70%.

[0147] 4) Synthesis of Compound M1: Under nitrogen environment, (14.2 g, 30 mmol) of Compound M1-6, (7.4 g, 30 mmol) of Compound M1-7, (0.55 g, 0.6 mmol) of Compound Pd2(dba)3, (0.24 g, 1.2 mmol) of Compound tri-tert-butylphosphine, (4.1 g, 45 mmol) of Compound sodium tert-butoxide and 100 mL of anhydrous toluene solvent were added to a 300 mL two-necked bottle, heated to 60°C, stirred for 6 hours, cooled to room temperature, quenched with water, and the reaction liquid was rotary evaporated to remove most of the solvent, dissolved in dichloromethane and washed 3 times, the organic liquid was collected and mixed with silica gel for column chromatography purification, and the yield was 85%. MS (ASAP): 638.

[0148] Example 2: Synthesis of compound (M2):

[0149]

[0150] 1) Synthesis of intermediate M2-2: Referring to the synthesis method of compound M1-5, compound M2-1 was substituted for compound M1-4.

[0151] 2) Synthesis of intermediate M2-3: Referring to the synthesis method of compound M1-6, compound M2-2 was substituted for compound M1-5, with a yield of 68%.

[0152] 3) Synthesis of compound M2: Referring to the synthesis method of compound M1, compounds M2-3 and M2-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 83%. MS (ASAP): 714.

[0153] Example 3: Synthesis of compound (M3):

[0154]

[0155] 1) Synthesis of Compound M3: Referring to the synthesis method of Compound M1, Compound M3-1 was substituted for Compound M1-7, with a yield of 81%. MS (ASAP): 612.

[0156] Example 4: Synthesis of compound (M4):

[0157]

[0158] 1) Synthesis of compound M4: Referring to the synthesis method of compound M1, compounds M2-3 and M4-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 712.

[0159] Example 5: Synthesis of compound (M5):

[0160]

[0161] 1) Synthesis of Compound M5: Referring to the synthesis method of Compound M1, Compound M5-1 was substituted for Compound M1-7, with a yield of 85%. MS (ASAP): 678.

[0162] Example 6: Synthesis of compound (M6):

[0163]

[0164] 1) Synthesis of intermediate M6-2: Referring to the synthesis method of compound M1-5, compound M6-1 was substituted for compound M1-4.

[0165] 2) Synthesis of intermediate M6-3: Referring to the synthesis method of compound M1-6, compound M6-2 was substituted for compound M1-5, with a yield of 72%.

[0166] 3) Synthesis of compound M6: Referring to the synthesis method of compound M1, compounds M6-3 and M6-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 80%. MS (ASAP): 666.

[0167] Example 7: Synthesis of compound (M7):

[0168]

[0169] 1) Synthesis of intermediate M7-2: Referring to the synthesis method of compound M1-5, compound M7-1 was substituted for compound M1-4.

[0170] 2) Synthesis of intermediate M7-3: Referring to the synthesis method of compound M1-6, compound M7-2 was substituted for compound M1-5, and the yield was 71%

[0171] 3) Synthesis of compound M7: Referring to the synthesis method of compound M1, compounds M7-3 and M7-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 732.

[0172] Example 8: Synthesis of compound (M8):

[0173]

[0174] 1) Synthesis of intermediate M8-2: Referring to the synthesis method of compound M1-5, compound M8-1 was substituted for compound M1-4.

[0175] 2) Synthesis of intermediate M8-3: Referring to the synthesis method of compound M1-6, compound M8-2 was substituted for compound M1-5, with a yield of 68%.

[0176] 3) Synthesis of compound M8: Referring to the synthesis method of compound M1, compounds M8-3 and M8-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 76%. MS (ASAP): 666.

[0177] Example 9: Synthesis of compound (M9):

[0178]

[0179] 1) Synthesis of Compound M9: Referring to the synthesis method of Compound M1, Compound M9-1 was substituted for Compound M1-7, with a yield of 82%. MS (ASAP): 665.

[0180] Example 10: Synthesis of compound (M10):

[0181]

[0182] 1) Synthesis of compound M10: Referring to the synthesis method of compound M1, compound M10-1 was substituted for compound M1-7, with a yield of 80%. MS (ASAP): 652.

[0183] Example 11: Synthesis of compound (M11):

[0184]

[0185] 1) Synthesis of compound M11: Referring to the synthesis method of compound M1, compounds M7-3 and M11-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 722.

[0186] Example 12: Synthesis of compound (M12):

[0187]

[0188] 1) Synthesis of compound M12: Referring to the synthesis method of compound M1, compounds M6-3 and M12-1 were used to replace compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 696.

[0189] Example 13: Synthesis of compound (M13):

[0190]

[0191] 1) Synthesis of compound M13: Referring to the synthesis method of compound M1, compounds M7-3 and M13-1 were used to replace compounds M1-6 and M1-7, respectively, with a yield of 84%. MS (ASAP): 750.

[0192] Example 14: Synthesis of compound (M14):

[0193]

[0194] 1) Synthesis of intermediate M14-3: Referring to the synthesis method of compound M1, compounds M14-2 and M14-1 were used to replace compounds M1-6 and M1-7, respectively, with a yield of 76%.

[0195] 2) Synthesis of compound M14: Referring to the synthesis method of compound M1, compounds M6-3 and M14-3 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 678.

[0196] Example 15: Synthesis of compound (M15):

[0197]

[0198] 1) Synthesis of compound M15-2: Referring to the synthesis method of compound M1-3, compound M15-1 was substituted for compound M1-2, with a yield of 72%.

[0199] 2) Synthesis of intermediate M15-3: Referring to the synthesis method of compound M1-5, compounds M15-2 and M6-1 were used to replace compounds M1-3 and M1-4, respectively.

[0200] 3) Synthesis of intermediate M15-4: Referring to the synthesis method of compound M1-6, compound M15-3 was substituted for compound M1-5, and the yield was 69%.

[0201] 4) Synthesis of compound M15: Referring to the synthesis method of compound M1, compounds M15-4 and M5-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 84%. MS (ASAP): 666.

[0202] Example 16: Synthesis of compound (M16):

[0203]

[0204] 1) Synthesis of compound M16-2: Referring to the synthesis method of compound M1-3, compound M16-1 was substituted for compound M1-2, with a yield of 75%.

[0205] 2) Synthesis of intermediate M16-3: Under nitrogen environment, (24.9 g, 60 mmol) of compound M16-2 and 150 mL of anhydrous tetrahydrofuran solvent were added to a 500 mL two-necked flask, stirred to dissolve, cooled to -78 ° C, 60 mmol of tert-butyl lithium was slowly added dropwise, the temperature was maintained, and the reaction was continued with stirring for 2 hours. The reaction solution was transferred to 100 mL of anhydrous tetrahydrofuran solution containing (11.9 g, 60 mmol) of compound M6-1, stirred at room temperature for 4 hours, quenched with water, and the reaction solution was rotary evaporated to remove most of the solvent, dissolved in dichloromethane and washed 3 times, the organic phase was collected, and it was directly used as the raw material for the next step after spin drying.

[0206] 3) Synthesis of intermediate M16-4: Referring to the synthesis method of compound M1-6, compound M16-3 was substituted for compound M1-5, with a yield of 68%.

[0207] 4) Synthesis of compound M16: Referring to the synthesis method of compound M1, compounds M16-4 and M16-5 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 85%. MS (ASAP): 650.

[0208] Example 17: Synthesis of compound (M17):

[0209]

[0210] 1) Synthesis of compound M17-2: Referring to the synthesis method of compound M1-3, compound M17-1 was substituted for compound M1-2, with a yield of 68%.

[0211] 2) Synthesis of intermediate M17-3: Referring to the synthesis method of compound M1-5, compound M17-2 was substituted for compound M1-3.

[0212] 3) Synthesis of intermediate M17-4: Referring to the synthesis method of compound M1-6, compound M17-3 was substituted for compound M1-5, with a yield of 70%.

[0213] 4) Synthesis of compound M17: Referring to the synthesis method of compound M1, compounds M17-4 and M16-5 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 83%. MS (ASAP): 678.

[0214] Example 18: Synthesis of compound (M18):

[0215]

[0216] 1) Synthesis of compound M18-2: Referring to the synthesis method of compound M1-3, compound M18-1 was substituted for compound M1-2, with a yield of 67%.

[0217] 2) Synthesis of intermediate M18-3: Referring to the synthesis method of compound M1-5, compound M18-2 was substituted for compound M1-3.

[0218] 3) Synthesis of intermediate M18-4: Referring to the synthesis method of compound M1-6, compound M18-3 was substituted for compound M1-5, with a yield of 68%.

[0219] 4) Synthesis of compound M18: Referring to the synthesis method of compound M1, compounds M18-4 and M18-5 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 84%. MS (ASAP): 652.

[0220] Example 19: Synthesis of compound (M19):

[0221]

[0222] 1) Synthesis of compound M19-2: Referring to the synthesis method of compound M1-3, compound M19-1 was substituted for compound M1-2, with a yield of 72%.

[0223] 2) Synthesis of intermediate M19-4: Under nitrogen environment, add (20.2 g, 60 mmol) compound M19-2 and 200 mL of anhydrous tetrahydrofuran into a 500 mL three-necked flask, stir to dissolve, cool to 0°C, slowly add 150 mmol of compound M19-3, continue to react for 6 hours, terminate the reaction, add pure water to quench the reaction, rotary evaporate most of the reaction solution, wash three times with dichloromethane, collect the organic phase, spin dry and use it directly as the raw material for the next step.

[0224] 3) Synthesis of intermediate M19-5: Referring to the synthesis method of compound M1-6, compound M19-4 was used instead of compound M1-5, with a yield of 65%.

[0225] 4) Synthesis of compound M19: Referring to the synthesis method of compound M1, compounds M19-5 and M2-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 85%. MS (ASAP): 590.

[0226] Example 20: Synthesis of compound (M20):

[0227]

[0228] 1) Synthesis of compound M20-2: Referring to the synthesis method of compound M1-3, compound M20-1 was substituted for compound M1-2, with a yield of 66%.

[0229] 2) Synthesis of intermediate M20-3: Referring to the synthesis method of compound M19-4, compound M20-2 was substituted for compound M19-2.

[0230] 3) Synthesis of intermediate M20-4: Referring to the synthesis method of compound M1-6, compound M20-3 was substituted for compound M1-5, and the yield was 67%.

[0231] 4) Synthesis of compound M20: Referring to the synthesis method of compound M1, compounds M20-4 and M4-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 81%. MS (ASAP): 588.

[0232] Example 21: Synthesis of compound (M21):

[0233]

[0234] 1) Synthesis of compound M21-2: Referring to the synthesis method of compound M1-3, compound M21-1 was substituted for compound M1-2, with a yield of 65%.

[0235] 2) Synthesis of intermediate M21-3: Referring to the synthesis method of compound M19-4, compound M21-2 was substituted for compound M19-2.

[0236] 3) Synthesis of intermediate M21-4: Referring to the synthesis method of compound M1-6, compound M21-3 was substituted for compound M1-5, with a yield of 63%.

[0237] 4) Synthesis of compound M21: Referring to the synthesis method of compound M1, compounds M21-4 and M21-5 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 75%. MS (ASAP): 630.

[0238] Example 22: Synthesis of compound (M22):

[0239]

[0240] 1) Synthesis of compound M22: Referring to the synthesis method of compound M1, compounds M20-4 and M22-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 653.

[0241] Example 23: Synthesis of compound (M23):

[0242]

[0243] 1) Synthesis of compound M23: Referring to the synthesis method of compound M1, compounds M20-4 and M23-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 83%. MS (ASAP): 708.

[0244] Example 24: Synthesis of compound (M24):

[0245]

[0246] 1) Synthesis of intermediate M24-2: Referring to the synthesis method of compound M19-4, compound M24-1 was substituted for compound M19-3.

[0247] 2) Synthesis of intermediate M24-3: Referring to the synthesis method of compound M1-6, compound M24-2 was substituted for compound M1-5, with a yield of 69%.

[0248] 3) Synthesis of compound M24: Referring to the synthesis method of compound M1, compounds M24-3 and M24-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 85%. MS (ASAP): 696.

[0249] Example 25: Synthesis of compound (M25):

[0250]

[0251] 1) Synthesis of compound M25-2: Referring to the synthesis method of compound M1-3, compound M25-1 was substituted for compound M1-2, with a yield of 68%.

[0252] 2) Synthesis of intermediate M25-3: Referring to the synthesis method of compound M19-4, compound M25-2 was substituted for compound M19-2.

[0253] 3) Synthesis of intermediate M25-4: Referring to the synthesis method of compound M1-6, compound M25-3 was substituted for compound M1-5, and the yield was 66%.

[0254] 4) Synthesis of intermediate M25-5: Add (12.8 g, 40 mmol) of compound M25-4, 50 mL of dimethylformamide (DMF) and 50 mL of dichloromethane into a 300 mL two-necked flask, stir to dissolve, slowly add dropwise 40 mmol of N-bromosuccinimide in DMF solution under ice bath, stir to react for 6 hours, after the reaction is completed, add water to quench, extract with dichloromethane, wash with water 3 times, collect the organic liquid, mix with silica gel and purify by column chromatography, the yield is 42%.

[0255] 5) Synthesis of compound M25: Referring to the synthesis method of compound M1, compounds M25-5 and M5-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 76%. MS (ASAP): 604.

[0256] Example 26: Synthesis of compound (M26):

[0257]

[0258] 1) Synthesis of compound M26-2: Referring to the synthesis method of compound M1-3, compound M26-1 was substituted for compound M1-2, with a yield of 67%.

[0259] 2) Synthesis of intermediate M26-3: Referring to the synthesis method of compound M19-4, compound M26-2 was substituted for compound M19-2.

[0260] 3) Synthesis of intermediate M26-4: Referring to the synthesis method of compound M1-6, compound M26-3 was substituted for compound M1-5, with a yield of 65%.

[0261] 4) Synthesis of intermediate M26-5: Add (15.5 g, 40 mmol) compound M26-4, 0.5 g iron powder and 100 mL chloroform into a 300 mL two-necked flask, stir to dissolve, slowly add dropwise 40 mmol bromine solution in chloroform under ice bath, stir to react for 4 hours, after the reaction is completed, add sodium bisulfate aqueous solution to quench, extract with dichloromethane, wash with water 3 times, collect the organic liquid and mix with silica gel for column chromatography purification, the yield is 75%.

[0262] 5) Synthesis of compound M26: Referring to the synthesis method of compound M1, compounds M26-5 and M2-4 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 82%. MS (ASAP): 706.

[0263] Example 27: Synthesis of compound (M27):

[0264]

[0265] 1) Synthesis of compound M27-2: Referring to the synthesis method of compound M1-3, compound M27-1 was substituted for compound M1-2, with a yield of 66%.

[0266] 2) Synthesis of intermediate M27-3: Referring to the synthesis method of compound M19-4, compound M27-2 was substituted for compound M19-2.

[0267] 3) Synthesis of intermediate M27-4: Referring to the synthesis method of compound M1-6, compound M27-3 was substituted for compound M1-5, with a yield of 68%.

[0268] 4) Synthesis of intermediate M27-5: Referring to the synthesis method of compound M26-5, compound M27-4 was substituted for compound M26-4, with a yield of 70%.

[0269] 5) Synthesis of compound M27: Referring to the synthesis method of compound M1, compounds M27-5 and M5-1 were substituted for compounds M1-6 and M1-7, respectively, with a yield of 77%. MS (ASAP): 660.

[0270] Example 28: Synthesis of compound (M28):

[0271]

[0272] 1) Synthesis of compound M28-2: Referring to the synthesis method of compound M1-3, compound M28-1 was substituted for compound M1-2, with a yield of 64%.

[0273] 2) Synthesis of intermediate M28-3: Referring to the synthesis method of compound M1-5, compounds M28-2 and M6-1 were used to replace compounds M1-3 and M1-4, respectively.

[0274] 3) Synthesis of intermediate M28-4: Referring to the synthesis method of compound M1-6, compound M28-3 was substituted for compound M1-5, with a yield of 67%.

[0275] 4) Synthesis of compound M28-5: Referring to the synthesis method of compound M1, compounds M28-4 and M5-1 were used to replace compounds M1-6 and M1-7, respectively, with a yield of 76%.

[0276] 5) Synthesis of compound M28: Under nitrogen, (19.5 g, 30 mmol) of compound M28-5, (5.1 g, 30 mmol) of compound M18-5, (0.43 g, 0.6 mmol) of compound dichloro-di-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II), (0.57 g, 1.2 mmol) of compound 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, (4.1 g, 45 mmol) of compound sodium tert-butoxide and 100 mL of anhydrous toluene solvent were added to a 300 mL two-necked flask, heated to 60°C, stirred for reaction for 6 hours, cooled to room temperature, quenched with water, and the reaction solution was rotary evaporated to remove most of the solvent, dissolved in dichloromethane and washed 3 times with water, and the organic solution was collected and mixed with silica gel for column chromatography purification, with a yield of 74%. MS (ASAP): 783.

[0277] 2. Preparation and characterization of OLED devices

[0278] Device Example 1: The preparation process of the above-mentioned OLED device is described in detail below through a specific example. The preparation steps are as follows:

[0279] 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 30nm and an evaporation rate of On the hole injection layer, the hole transport material HT is vacuum deposited to a thickness of 60nm. On the hole transport layer, an electron blocking material is evaporated to form an electron blocking layer, wherein the electron blocking material uses the compound M1 obtained in Example 1, and the thickness is 10nm. On the electron blocking layer, a light-emitting layer is evaporated, RH is used as the main material, RD is used as the doping material, the mass ratio of RD and RH is 3:100, and the thickness is 40nm. On the light-emitting layer, electron transport materials ET and Liq are vacuum deposited by vacuum evaporation, with a mass ratio of 5:5 and a thickness of 30nm. On the electron transport layer, the electron injection layer Liq is vacuum evaporated to a thickness of 1nm. On the electron injection layer, a cathode Al layer is vacuum evaporated to a thickness of 100nm.

[0280] Device Examples 2 to 28: Compounds M2 to M28 are used as electron blocking layer materials for organic electroluminescent devices. For details, see Table 1. They replace M1 in Device Example 1 respectively, and other conditions remain unchanged.

[0281] The structures of the compounds involved in the device are as follows:

[0282] Comparative Examples 1-2: The electron blocking layer material of the organic electroluminescent device is made of comparative compounds Ref-1 and Ref-2, which respectively replace M1 in device Example 1, and other conditions remain unchanged.

[0283] The structures of the compounds involved in the device are as follows:

[0284]

[0285] The characterization equipment was used to test the current-voltage (JV) characteristics of the organic light-emitting diodes of the red light device embodiments M1 to M28 and comparative examples 1 to 2, and important parameters such as efficiency, life (see Table 1) and external quantum efficiency were recorded. In Table 1, all external quantum efficiencies and lifespans are relative values ​​to the organic light-emitting diode of comparative example 1. It can be seen that the efficiency and lifespan of the embodiments of the present invention are significantly improved. It can be seen that the red light device prepared based on the compounds of the present invention has been greatly improved in terms of efficiency and lifespan.

[0286] Table 1

[0287]

[0288]

[0289] The luminous efficiency in Table 1 is the current density of 10mA / cm 2 As can be seen from Table 1: compared with comparative examples 1 and 2, the compounds of the present invention have more cyclopentane groups, which can better regulate the transmission of holes and the charge transfer balance in the device. As an electron blocking layer, the compounds of the present invention can more effectively improve the luminous efficiency and life of the organic electroluminescent device.

[0290] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0291] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope 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, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An organic compound, characterized in that It has a structure as shown in the general formula (1): Wherein: Ar1 is selected from one of the following groups: Wherein: Y represents a member selected from NR2, CR3R4, O, S, SiR3R4 or PR2; The Ar2 is selected from one or a combination of the following groups: Ar3-Ar6 are independently selected from one or a combination of the following groups: in: X, at each occurrence, is independently selected from CR5 or N; Z, at each occurrence, is independently selected from NR6, CR7R8, SiR7R8, O, S or PR6; L1 is selected from an unsubstituted aromatic group having 6 to 60 ring atoms, or an unsubstituted heteroaromatic group having 5 to 60 ring atoms; L2 is selected from one of the following groups: Wherein, e represents an integer from 0 to 5, and * represents a connection site; R0 is selected from D, or a straight-chain alkyl group having 1 to 10 C atoms, or a branched-chain alkyl group having 3 to 10 C atoms, or a cyclic alkyl group having 3 to 10 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, I, or an aromatic group having 6 to 10 ring atoms, or a heteroaromatic group having 6 to 10 ring atoms; R1-R8, at each occurrence, is independently selected from -H, -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy 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 cyclic alkyl group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, an amine group, -CF3, -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20 C atoms, or an unsubstituted aromatic group having 6 to 30 ring atoms, or an unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a combination of these groups; Adjacent R1s may or may not form a ring with each other; R3 and R4 may or may not form a ring with each other; a is 0, b is independently selected from 1 or 2; c is selected from 0, 1, 2, 3 or 4; n and m are selected from 0 or 1, and n+m is greater than or equal to 1.

2. The organic compound according to claim 1, characterized in that The organic compound has a structure as shown in any one of the general formulas (1-1) to (1-7):

3. The organic compound according to claim 1, characterized in that The organic compound has a structure as shown in any one of the general formulas (2-1) to (2-15):

4. The organic compound according to claim 1, characterized in that Ar3 is selected from and / or Ar5 is selected from 5. The organic compound according to claim 4, characterized in that In the general formula (1), Each is independently selected from one of the following structures: Among them: the above groups are unsubstituted or replaced by R 0 replace; R 0 is selected from -D, or a straight-chain alkyl group having 1 to 10 C atoms, or a branched-chain alkyl group having 3 to 10 C atoms, or a cyclic alkyl group having 3 to 10 C atoms, or a silyl group, a cyano group, an isocyano group, a hydroxyl group, a nitro group, -CF3, -Cl, -Br, -F, -I, or an aromatic group having 6 to 10 ring atoms, or a heteroaromatic group having 6 to 10 ring atoms.

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

7. A mixture, characterized in that The invention comprises the organic compound according to any one of claims 1 to 6, and at least one organic functional material.

8. A composition, characterized in that The method comprises the 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, characterized in that: The invention comprises a first electrode, a second electrode and one or more organic functional layers located between the first electrode and the second electrode, wherein at least one of the organic functional layers comprises the organic compound according to any one of claims 1 to 6, or the mixture according to claim 7, or is prepared from the composition according to claim 8.

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