A compound and its application in organic optoelectronic devices

Abstract

The invention discloses a compound and its application in an organic optoelectronic device, the compound having a structure as shown in formula (1), L1-L3 independently selected from a single bond, substituted or unsubstituted C6-C30 aryl or C5-C30 heteroaryl; A1-A3 independently selected from a single bond, substituted or unsubstituted chain alkylene or chain alkylene with branch, cycloalkylene or heterocycloalkylene, alkyl imine, alkylene ether, alkylene thioether, arylene, sub-heteroaryl, arylene imine, arylene ether, arylene thioether, heteroarylene imine, sub-heteroaryl ether, sub-heteroaryl thioether; Ar1-Ar3 independently selected from substituted or unsubstituted C6-C30 aryl or C5-C30 heteroaryl, and at least one selected from a group as shown in formula (2). The compound of the present invention can effectively improve the luminous efficiency and service life of the device as a hole transport material of an OLED device.

Description

Technical Field

[0001] The invention relates to the field of organic photoelectric materials, and in particular to a compound and application thereof in an organic photoelectric device. Background Art

[0002] Organic electroluminescent (OLED) devices are a type of device with a sandwich-like structure, including positive and negative electrode film layers and organic functional material layers sandwiched between the electrode film layers. Currently, this technology has been widely used in display panels of new lighting fixtures, smart phones, tablet computers and other products, and will further expand to large-size display products such as televisions. It is a new display technology that is developing rapidly and has high technical requirements.

[0003] Common functional organic materials used in OLED devices include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guest (dyes), etc. Based on this, the OLED material field has been committed to developing new organic electroluminescent materials to achieve low device startup voltage, high luminous efficiency and better service life. So far, the development of existing OLED optoelectronic functional materials is far behind the performance requirements of panel manufacturers for OLED materials, so it is particularly urgent to develop organic functional materials with better performance to meet the current needs of industrial development.

[0004] At present, hole transport materials mainly use aromatic amine compounds with good hole transport properties. N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) is widely used in organic electroluminescent devices with various colors of light due to its moderate highest occupied orbital energy level and good hole mobility. However, the glass transition temperature of this molecule is low (98°C), and the device is prone to phase change under the action of accumulated Joule heat when working for a long time, which has a great impact on the life of the device. Therefore, it is necessary to design hole transport materials with both high mobility and glass transition temperature. Summary of the invention

[0005] Based on this, the present invention introduces alkyl derivatives into the triarylamine system to obtain a series of compounds with excellent performance, wherein the introduction of benzoalkane derivatives is not only conducive to improving the stability of molecular fragments, but also increases the molecular weight, thereby increasing the glass transition temperature of the molecule. In addition, in order to obtain compounds with high triplet energy levels, chain or cyclic alkane compounds are directly introduced into the molecular system, which can interrupt the conjugation between molecules and reduce the conjugation range, thereby obtaining products with high triplet energy levels. At the same time, the alkyl group has a stronger electron donation ability than the aryl group, which can improve the electron donation characteristics of the molecule and enhance the electron transmission ability, and the benzocycloalkyl compound has a strong rigidity, making the molecule more stable. This type of compound can provide strong efficiency and life for organic electroluminescent devices as hole transport materials for OLED devices.

[0006] To achieve the above object, the present invention provides a compound having a chemical structure as shown in formula (1):

[0007]

[0008] In formula (1), L1-L3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C5-C30 heteroaryl group;

[0009] A1-A3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C2-C24 chain alkylene group, a substituted or unsubstituted C2-C24 branched chain alkylene group, a substituted or unsubstituted C3-C18 cycloalkylene group, a substituted or unsubstituted C3-C18 heterocycloalkylene group, a substituted or unsubstituted C2-C24 alkylimine group, a substituted or unsubstituted C2-C24 alkylene ether group, a substituted or unsubstituted C2-C30 alkylene thioether group, a substituted or unsubstituted C6-C30 arylene group , substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C6-C30 aryl imine, substituted or unsubstituted C6-C30 arylene ether, substituted or unsubstituted C2-C24 arylene thioether, substituted or unsubstituted C5-C30 heteroaryl imine, substituted or unsubstituted C5-C30 heteroarylene ether, substituted or unsubstituted C2-C24 heteroarylene thioether, and at least one of A1-A3 is selected from C2-C24 alkylene, substituted or unsubstituted C3-C18 cycloalkylene;

[0010] Ar1-Ar3 are the same or different, and are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C5-C30 heteroaryl groups, and at least one of Ar1-Ar3 is selected from at least one of the groups represented by the following formula (2):

[0011]

[0012] In formula (2), Z1-Z9 are each independently selected from C(R1R2), N(R3), O or S;

[0013] Ar is selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl;

[0014] R1-R3 are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C3-C18 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.

[0015] Another aspect of the present invention provides an organic layer comprising the aforementioned compound of the present invention.

[0016] Another aspect of the present invention provides use of the aforementioned compound or the aforementioned organic layer of the present invention in an organic optoelectronic device.

[0017] Another aspect of the present invention provides an organic photoelectric device, which comprises a first electrode, a second electrode and the organic layer as described above in the present invention, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer.

[0018] Another aspect of the present invention provides a display or lighting device, comprising the organic photoelectric device as described above in the present invention.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: the compound provided by the present invention introduces a benzoalkyl group to make the structure more stable, and introduces a chain or cyclic alkyl group to reduce the conjugation of the compound, which improves the triplet energy level of the compound, and the alkyl group has better electron transport ability than the aromatic group, so that the overall compound has good hole transport performance and thermal stability. The compound of the present invention is applied to an organic optoelectronic device so that the device has a higher hole mobility, and can effectively block electrons and excitons from entering the hole transport layer, thereby improving the efficiency of the device, and the high stability of the molecule further improves the luminous efficiency and service life of the device. DETAILED DESCRIPTION

[0020] The present invention provides a compound having a chemical structure as shown in formula (1):

[0021]

[0022] In formula (1), L1-L3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C5-C30 heteroaryl group;

[0023] A1-A3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C2-C24 chain alkylene group, a substituted or unsubstituted C2-C24 branched chain alkylene group, a substituted or unsubstituted C3-C18 cycloalkylene group, a substituted or unsubstituted C3-C18 heterocycloalkylene group, a substituted or unsubstituted C2-C24 alkylimine group, a substituted or unsubstituted C2-C24 alkylene ether group, a substituted or unsubstituted C2-C30 alkylene thioether group, a substituted or unsubstituted C6-C30 arylene group , substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C6-C30 aryl imine, substituted or unsubstituted C6-C30 arylene ether, substituted or unsubstituted C2-C24 arylene thioether, substituted or unsubstituted C5-C30 heteroaryl imine, substituted or unsubstituted C5-C30 heteroarylene ether, substituted or unsubstituted C2-C24 heteroarylene thioether, and at least one of A1-A3 is selected from C2-C24 alkylene, substituted or unsubstituted C3-C18 cycloalkylene;

[0024] Ar1-Ar3 are the same or different, and are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C5-C30 heteroaryl groups, and at least one of Ar1-Ar3 is selected from at least one of the groups represented by the following formula (2):

[0025]

[0026] In formula (2), Z1-Z9 are each independently selected from C(R1R2), N(R3), O or S;

[0027] Ar is selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl;

[0028] R1-R3 are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C3-C18 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.

[0029] Examples of substituents in the present invention are described below, but the substituents are not limited thereto:

[0030] [Substituted or unsubstituted] means substituted with one or more substituents selected from the group consisting of deuterium, halogen, nitrile, nitro, hydroxyl, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamine, arylamine, arylphosphino and heteroaryl, acenaphthenyl, or unsubstituted; or substituted with a substituent connecting two or more of the substituents exemplified above, or unsubstituted; for example, "a substituent connecting two or more substituents" may include a biphenyl group, i.e., the biphenyl group may be an aryl group, or a substituent connecting two phenyl groups.

[0031] [Alkyl] may be straight chain or branched, and the number of carbon atoms is not particularly limited. In some embodiments, alkyl includes but is not limited to methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl.

[0032] The above description of the alkyl group also applies to the alkyl group in the aralkyl group, aralkylamino group, alkylaryl group and alkylamino group.

[0033] [Heteroalkyl] can be a straight or branched alkyl containing heteroatoms, and the number of carbon atoms is not particularly limited. In some embodiments, heteroalkyl includes but is not limited to alkoxy, alkylthio, alkylsulfonyl, alkoxy includes but is not limited to methoxy, ethoxy, n-propoxy, isopropoxy, isopropoxy, n-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy; alkylthio includes but is not limited to methylthio, ethylthio, n-propylthio, isopropylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, sec-butylthio, n-pentylthio, neopentylthio, isopentylthio, n-hexylthio, 3,3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio; alkylthio includes but is not limited to methylthio, ethylthio, n-propylthio, isopropylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, sec-butylthio, n-pentylthio, neopentylthio, isopentylthio, n-hexylthio, 3,3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio.

[0034] [Cycloalkyl] may be cyclic, and the number of carbon atoms is not particularly limited. In some embodiments, cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

[0035] [Heterocycloalkyl] may be a cycloalkyl group containing heteroatoms, and the number of carbon atoms is not particularly limited. In some embodiments, heterocycloalkyl groups include but are not limited to wait.

[0036] [Aryl] There is no particular limitation, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, the monocyclic aryl group includes, but is not limited to, phenyl, biphenyl, terphenyl, quaterphenyl, pentaphenyl, and the like. Polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, and the like. The fluorenyl group may be substituted, such as 9,9'-dimethylfluorenyl, 9,9'-dibenzofluorenyl, and the like. In addition, two of the substituents may be combined with each other to form a spiro ring structure, such as 9,9'-spirobifluorenyl, and the like.

[0037] The above description of the aryl group can be applied to the arylene group, except that the arylene group is divalent.

[0038] The above description of the aryl group may be applied to the aryl group in the aryloxy group, arylthio group, arylsulfonyl group, arylphosphino group, arylalkyl group, arylalkylamino group, arylalkenyl group, alkylaryl group, arylamino group and arylheteroarylamino group.

[0039] [Heteroaryl] contains one or more of N, O, P, S, Si and Se as heteroatoms. Heteroaryl includes, but is not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, azinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, dihydroindole, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazine pyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolecarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazoquinazolinyl, benzimidazophenanthridinyl, spiro[fluorene-9,9'-xanthene], benzobinaphthyl, dinaphthofuranyl, naphthiobenzofuranyl, dinaphthothiophene, naphthiobenzothiophene, triphenylphosphine oxide, triphenylborane.

[0040] The above description of the heteroaryl group may be applied to the heteroaryl group in the heteroarylamine group and the arylheteroarylamine group.

[0041] The above description of heteroaryl groups applies to heteroarylene groups, except that the heteroarylene group is divalent.

[0042] Specifically, the aforementioned compounds of the present invention may be unsubstituted or substituted with one or more substituents selected from the following. For example, they may be deuterium, halogen, nitrile, nitro, hydroxyl, carbonyl, ester, imido, amine, phosphine oxide, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, arylheteroarylamino, arylphosphino and heteroaryl.

[0043] In some embodiments, at least one of A1-A3 in formula (1) is selected from at least one of the groups shown in formula (3):

[0044]

[0045] In formula (3), X1-X m The same or different, each independently selected from C(R 16 R 17 )、N(R 18 ), O or S, m≥4 and is an integer;

[0046] Y is selected from C(R 19 R 20 )、N(R 21 ), O or S;

[0047] R4-R 21 are the same or different, and are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C3-C18 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or bonded to adjacent atoms to form a ring;

[0048] n ≥ 1 and is an integer, and * is the connection site of the atom.

[0049] In formula (1), the carbon number of the aforementioned alkyl group may be 1-10, 1-20 or 20-30; the carbon number of the aforementioned cycloalkyl group may be 3-10, 3-20 or 3-30; the carbon number of the aforementioned heteroalkyl group may be 3-10, 1-20 or 20-30; the carbon number of the aforementioned heterocycloalkyl group may also be 3-10, 3-20 or 20-30; the carbon number of the aforementioned aryl group may be 6-10, 6-20 or 20-30; the carbon number of the aforementioned heteroaryl group may be 6-10, 6-20 or 20-30.

[0050] In some embodiments, L1-L3 in formula (1) are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl,

[0051] In some embodiments, the compound described in formula (1) is selected from the following chemical structures:

[0052]

[0053]

[0054]

[0055]

[0056] Another aspect of the present invention provides an organic layer comprising the aforementioned compound of the present invention.

[0057] Another aspect of the present invention provides use of the aforementioned compound and / or the aforementioned organic layer of the present invention in an organic optoelectronic device.

[0058] The organic photoelectric device provided by the present invention includes a first electrode, a second electrode, and one or more organic layers arranged between the first electrode and the second electrode, and is a bottom or top light-emitting device structure. The organic layer can be a single-layer structure or a multi-layer series structure in which two or more organic layers are laminated. If the organic layer has at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer, it can be prepared using common methods and materials for preparing organic photoelectric devices. The organic photoelectric device of the present invention uses a compound as the organic layer of the organic photoelectric device.

[0059] In the organic photoelectric device provided by the present invention, the first electrode serves as an anode layer, and the anode material can be, for example, a material with a large work function so that holes can be smoothly injected into the organic layer, such as metals, metal oxides, a combination of metals and oxides, conductive polymers, etc. Metal oxides include indium tin oxide (ITO), zinc oxide, indium oxide, and indium zinc oxide (IZO).

[0060] In the organic photoelectric device provided by the present invention, the second electrode serves as a cathode layer. The cathode material may be, for example, a material having a small work function so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multilayer structure material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin and lead or an alloy thereof. The cathode material is preferably magnesium and silver.

[0061] In the organic optoelectronic device provided by the present invention, the material of the hole injection layer is preferably a material whose highest occupied molecular orbital (HOMO) is between the work function of the anode material and the HOMO of the surrounding organic layer as a material that is advantageous for receiving holes from the anode at low voltage.

[0062] In the organic optoelectronic device provided by the present invention, the material of the hole transport layer is a material having high mobility for holes and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light-emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both a conjugated part and a non-conjugated part, and the like.

[0063] In the organic photoelectric device provided by the present invention, the compound provided by the present invention can be applied to the light-emitting layer of the device.

[0064] In the organic photoelectric device provided by the present invention, the material of the electron transport layer is a material having high mobility for electrons, and is suitable as a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer.

[0065] In the organic photoelectric device provided by the present invention, the material of the cover layer generally has a high refractive index, and thus can help improve the light efficiency of the organic light-emitting device, especially help improve the external light-emitting efficiency.

[0066] In the organic photoelectric device provided by the present invention, the organic photoelectric device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor, etc.

[0067] Another aspect of the present invention provides a display or lighting device, comprising the organic optoelectronic device of the present invention.

[0068] The synthesis of the compound represented by the above formula (1) can be carried out using known methods, such as cross-coupling reactions using transition metals such as nickel and palladium. Other synthesis methods are CC and CN coupling reactions using transition metals such as magnesium or zinc. The above reactions are limited to the characteristics of mild reaction conditions and superior selectivity of various functional groups, and preferably Suzuki and Buchwald reactions. The compounds of the present invention are illustrated by the following examples, but are not limited to the compounds and synthesis methods illustrated in these examples. The starting materials and solvents of the present invention and some commonly used OLED intermediates and other products were purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands, etc. were purchased from Sigma-Aldrich, 1 The H NMR data were measured using a JEOL (400 MHz) nuclear magnetic resonance spectrometer, and the HPLC data were measured using a Shimadzu LC-20AD high performance liquid chromatograph.

[0069] The substances used in the examples are:

[0070]

[0071] Example 1

[0072] Synthesis of compound 1

[0073]

[0074] 1) Synthesis of intermediate 1-1

[0075] Under argon atmosphere, 26.1 g (100 mmol) of compound 1-A, 16.9 g (100 mmol) of compound 1-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bis(dibenzylideneacetonepalladium), 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate and 1000 mL of xylene were added to the reaction vessel, and the mixture was heated and stirred at 140° C. for 15 hours. The reaction mixture was cooled to room temperature, 1000 ml of water was added, filtered, the filter cake was washed with a large amount of water, vacuum dried, and the crude product was refined by silica gel column chromatography (eluent: ethyl acetate / n-hexane) to obtain 24.4 g of compound 1-1, HPLC purity 99.6%, yield 70%. LC MS: M / Z 349.18(M+); 1H NMR(400MHz,DMSO-d6)δ2.59–2.70(m,2H),2.77(m,2H),7.02(s,1H),7.05–7.15(m,4H),7.22(m,3 H),7.22–7.33(m,2H),7.34–7.43(m,1H),7.43–7.54(m,4H),7.57–7.65(m,2H),7.69–7.77(m,2H).

[0076] 2) Synthesis of Compound 1

[0077] Under argon atmosphere, 34.9 g (100 mmol) of compound 1-1, 41.9 g (100 mmol) of compound 1-C, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bis(dibenzylideneacetonepalladium), 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate and 1000 mL of xylene were added to the reaction vessel, and heated and stirred at 140° C. for 15 hours. The reaction mixture was cooled to room temperature, 1000 ml of water was added, filtered, the filter cake was washed with a large amount of water, vacuum dried, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane) to obtain 51.6 g of compound 1, HPLC purity 99.9%, yield 75%. LCMS: M / Z 687.39 (M+).

[0078] 1H NMR(400MHz,DMSO-d6)δ1.22(s,12H),1.48(s,4H),2.59–2.70(m,2H),2.72–2.83(m,2H),6.67(m,1H),7.07–7.1 8(m,4H),7.18–7.31(m,6H),7.31–7.58(m,12H),7.69–7.76(m,2H),7.76–7.83(m,2H),7.88(d,1H),7.96(d,1H).

[0079] Example 2

[0080] Synthesis of compound 12

[0081]

[0082] Except that the starting materials were replaced with 12-A, 12-B and 21-C, the others were the same as Example 1. LC MS: M / Z 819.44 (M+). HPLC purity: 99.9%, total yield: 50%; 1 H NMR(400MHz,DMSO-d6)δ0.91(s,12H),1.72(d,12H),1.80(s,2H),6.91(m,1H),7.10–7.41(m,15H),7.36–7.51 (m,5H),7.51–7.58(m,3H),7.68(m,1H),7.75–7.83(m,2H),7.88(d,1H),7.93–8.01(m,2H),8.01–8.06(m,1H).

[0083] Example 3

[0084] Synthesis of compound 17

[0085]

[0086] Except that the starting materials were replaced with 17-B and 17-C, the other steps were the same as in Example 1. LC MS: M / Z 720.35 (M+). Total yield of synthesis: 52%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ1.66–1.83(m,4H),2.58–2.71(m,3H),2.66–2.76(m,3H),2.71–2.84(m,2H),6.67(m,1H),7.06–7 .43(m,18H),7.43–7.57(m,3H),7.58–7.68(m,3H),7.68–7.78(m,2H),7.78–7.88(m,2H),8.15–8.25(m,2H),8.66(d,1H).

[0087] Example 4

[0088] Synthesis of compound 23

[0089]

[0090] Except that the starting materials were replaced with 23-A, 12-B and 23-C, the others were the same as Example 1. LC MS: M / Z 763.38 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ1.69(s,12H),2.07(m,2H),2.77–2.99(m,4H),6.91(m,1H),7.06–7.51(m,21H) ,7.51–7.58(m,2H),7.68(m,1H),7.75–7.83(m,2H),7.88(d,1H),7.93–8.01(m,2H),8.01–8.06(m,1H).

[0091] Example 5

[0092] Synthesis of compound 32

[0093]

[0094] Except that the starting materials were replaced with 32-A, 32-B and 32-C, the others were the same as Example 1. LC MS: M / Z 807.48 (M+). Total yield of synthesis: 51%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ0.91(s,12H),1.35(s,12H),1.48(s,4H),1.69(s,6H),6.67(m,1H),6.98(m,1H),7.03–7.14(m, 4H),7.18–7.26(m,2H),7.30–7.50(m,12H),7.50–7.56(m,1H),7.82–7.91(m,2H),8.06–8.15(m,2H),8.15–8.24(m,2H).

[0095] Example 6

[0096] Synthesis of compound 43

[0097]

[0098] Except that the starting materials were replaced with 43-A, 12-B and 43-C, the others were the same as Example 1. LC MS: M / Z 747.48 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ0.91(s,12H),1.05–1.36(m,16H),2.79(m,1H),3.41–3.55(m,2H),6.67(m,1H),7.00–7.08(m,2H),7.11 –7.18(m,4H),7.18–7.27(m,6H),7.27–7.38(m,8H),7.34–7.43(m,1H),7.43–7.53(m,2H),7.50–7.58(m,4H),7.69–7.77(m,2H).

[0099] Example 7

[0100] Synthesis of compound 50

[0101]

[0102] Except that the starting materials were replaced with 50-A, 12-B and 50-C, the others were the same as Example 1. LC MS: M / Z 643.29 (M+). Total yield of synthesis: 58%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ1.05–1.23(m,4H),2.19–2.37(m,4H),3.23(m,2H),3.48(m,2H) ),4.57–4.65(m,2H),6.87–6.96(m,2H),7.00–7.08(m,2H),7.11–7.18(m,2H),7.18–7 .26(m,3H),7.26–7.37(m,3H),7.34–7.44(m,1H),7.40–7.52(m,5H),7.49–7.58(m,2H ),7.68(m,1H),7.75–7.83(m,2H),7.88(d,1H),7.93–8.01(m,2H),8.01–8.06(m,1H).

[0103] Example 8

[0104] Synthesis of compound 60

[0105]

[0106] Except that the starting materials were replaced with 60-A, 12-B and 60-C, the others were the same as Example 1. LC MS: M / Z 793.36 (M+). Total yield of synthesis: 52%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ1.72(s,12H),1.90–2.08(m,4H),2.15–2.27(m,1H),2.31(m,2H),2.79(m,2H),6.11 (s,2H),6.91(m,1H),6.94(m,1H),7.10–7.26(m,12H),7.26–7.54(m,11H),7.79(m,2H),7.92–7.98(m,3H).

[0107] Example 9

[0108] Synthesis of compound 77

[0109]

[0110] Except that the starting materials were replaced with 23-A, 12-B and 77-C, the others were the same as Example 1. LC MS: M / Z 803.41 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ1.69(s,18H),2.07(s,2H),2.77–2.90(m,4H),6.91(m,1H),7.05–7.5 8(m,23H),7.68(m,1H),7.74(d,1H),7.84–7.92(m,1H),7.94–8.01(m,1H),8.01–8.06(m,1H).

[0111] Example 10

[0112] Synthesis of compound 90

[0113]

[0114] Except that the starting materials were replaced with 90-A, 12-B and 90-C, the others were the same as Example 1. LC MS: M / Z 871.37 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ1.72(s,6H),1.95–2.11(m,4H),5.15–5.23(m,2H),6.11(s,2H),6.91(m,1H),6.97–7.06(m,2H),7.10–7.20(m,4H),7.2 3(s,4H),7.26–7.43(m,5H),7.38–7.51(m,7H),7.51–7.60(m,3H),7.61 –7.72(m,3H),7.75–7.83(m,2H),7.94–8.01(m,1H),8.01–8.09(m,3H).

[0115] Embodiment 11

[0116] Synthesis of compound 94

[0117]

[0118] Except that the starting materials were replaced with 94-A, 94-B and 94-C, the others were the same as Example 1. LC MS: M / Z 805.44 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ1.22(s,12H),1.48(s,4H),2.10(s,3H),3.60(t,2H),3.70–3.74(m,2H),6.6 7(m,1H),7.14–7.43(m,16H),7.43–7.68(m,10H),7.69–7.77(m,2H),8.17–8.27(m,2H),8.66(d,1H).

[0119] Example 12

[0120] Synthesis of compound 97

[0121]

[0122] Except that the starting materials were replaced with 97-A and 43-C, the rest was the same as Example 1. LC MS: M / Z 683.41 (M+). Total yield of synthesis: 52%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ1.22(s,12H),1.46–1.52(m,16H),6.67(m,1H),7.14–7.29( m,6H),7.29–7.39(m,7H),7.35–7.43(m,1H),7.43–7.58(m,8H),7.69–7.77(m,2H).

[0123] Embodiment 13

[0124] Synthesis of compound 104

[0125]

[0126] 1) Synthesis of Intermediate 104-1

[0127] Under argon atmosphere, add 26.1 g (100 mmol) of compound 104-A, 33.8 g (200 mmol) of compound 1-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bis(dibenzylideneacetonepalladium), 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate and 1000 mL of xylene to the reaction vessel, and heat and stir at 140°C for 15 hours. The reaction mixture is cooled to room temperature, 1000 ml of water is added, filtered, the filter cake is washed with a large amount of water, vacuum dried, and the crude product is purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane) to obtain 33.6 g of compound 104-1, HPLC purity 99.6%, yield 65%. LC MS: M / Z 516.26 (M+). 1H NMR(400MHz, DMSO-d6)δ2.65(d,4H),7.02(s,2H),7.05–7.15(m,8H),7.34–7.43(m,2H),7.43–7.54(m,8H),7.57–7.65(m,4H),7.69–7.77(m,4H).

[0128] 2) Synthesis of Compound 1

[0129] Under argon atmosphere, 51.7 g (100 mmol) of compound 104-1, 52.4 g (200 mmol) of compound 104-C, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bis(dibenzylideneacetonepalladium), 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate and 1000 mL of xylene were added to the reaction vessel, and the mixture was heated and stirred at 140° C. for 15 hours. The reaction mixture was cooled to room temperature, 1000 ml of water was added, filtered, the filter cake was washed with a large amount of water, vacuum dried, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane) to obtain 62.2 g of compound 1, HPLC purity 99.9%, yield 70%. LC MS: M / Z 888.54 (M+). 1 H NMR(400MHz,DMSO-d6)δ1.23(s,24H),1.48(s,8H),2.65(d,4H),6.45(m,2H),7.00(d,2H),7.05–7.19(m,10H),7.30–

[0130] 7.38(m,4H),7.34–7.43(m,2H),7.43–7.53(m,4H),7.50–7.58(m,4H),7.69–7.77(m,4H).

[0131] Embodiment 14

[0132] Synthesis of compound 113

[0133]

[0134] Except that the starting materials were replaced with 113-A, 113-B and 113-C, the rest was the same as Example 13. LC MS: M / Z 889.53 (M+). Total yield of synthesis: 43%; HPLC purity: 99.9%. 1H NMR(400MHz,DMSO-d6)δ1.23(s,24H),1.80(s,3H),2.10(s,3H),3.60(t,4H),6.95–7.0 4(m,2H),7.04–7.12(m,4H),7.14–7.29(m,9H),7.30–7.44(m,10H),7.50–7.58(m,8H).

[0135] Embodiment 15

[0136] Synthesis of compound 121

[0137]

[0138] Except that the starting material was replaced with 121-A, the other steps were the same as Example 13. LC MS: M / Z 886.62 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%. 1 H NMR(400MHz,DMSO-d6)δ0.91(s,24H),1.13(m,2H),1.48–1.73(m,24H),2.50–2.64(m,2H),6.45(m,2H) ,7.00(d,2H),7.08(d,2H),7.30–7.42(m,6H),7.37–7.43(m,1H),7.43–7.58(m,9H),7.69–7.77(m,4H).

[0139] Device Example 1: Preparation of an organic electroluminescent device

[0140]

[0141] The preparation process is as follows: on a glass substrate, a transparent anode ITO film layer (thickness 150nm) is formed to obtain a first electrode as an anode. Subsequently, a mixed material of compound T-1 and compound T-2 is evaporated on the surface of the anode as a hole injection layer by a vacuum evaporation method, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10nm. Subsequently, a 100nm thick compound T-2 is evaporated on the hole injection layer to obtain a first hole transport layer. Subsequently, a 10nm thick compound 1 of the present invention is evaporated on the first hole transport layer to obtain a second hole transport layer. On the second hole transport layer, compound T-3 and compound T-4 are co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer with a thickness of 40nm. Then, on the organic light-emitting layer, compound T-5 is sequentially evaporated to form a hole blocking layer (thickness 10nm), and compound T-6 and LiQ with a mixing ratio of 4:6 (mass ratio) form an electron transport layer (thickness 30nm). Finally, magnesium (Mg) and silver (Ag) are mixed at a deposition rate of 1:9 and vacuum deposited on the electron injection layer as the second electrode 109, thereby completing the manufacture of the organic light-emitting device.

[0142] Device Examples 2-15

[0143] An organic electroluminescent device was prepared in the same manner as in Device Example 1, except that Compounds 12, 17, 23, 32, 43, 50, 60, 77, 90, 94, 97, 104, 113 and 121 were used to replace Compound 1 when forming the second hole transport layer.

[0144] Device Comparison Example 1-2

[0145] The organic electroluminescent device was prepared in the same manner as in Device Example 1, except that Compound HT-1 and Compound HT-2 were used to replace Compound 1 when forming the second hole transport layer.

[0146] The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated by a computer-controlled Keithley 2400 test system, and the device life under dark conditions was obtained using a Polaronix (McScience Co.) life measurement system equipped with a power supply and a photodiode as a detection unit. Each group of device embodiments and device comparative example 1 were produced and tested in the same batch as the devices of device comparative example 2. The operating voltage, efficiency and life of the device of device comparative example 1 were respectively recorded as 1, and the ratios of the corresponding indicators of device embodiments 1-25 and the device comparative examples to the device comparative example 1 were calculated, as shown in Table 1.

[0147] Table 1

[0148]

[0149]

[0150] According to the results in Table 1, when used as the second hole transport layer of the light-emitting device, the compounds used in device embodiments 1-15 have lower voltages, higher luminous efficiencies, and significantly improved lifespans compared to the devices formed by the compounds used in device comparison examples 1-2.

[0151] Accordingly, the application of the compounds of the present invention to organic optoelectronic devices can enable the devices to have higher hole mobility and can effectively block electrons and excitons from entering the hole transport layer, thereby improving the efficiency of the device. At the same time, the molecules have high stability, which can further improve the luminous efficiency and service life of the device, and have great application value.

[0152] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A compound selected from the following chemical structures:

2. An organic layer comprising one or more of the compounds according to claim 1.

3. Use of the compound according to claim 1 or the organic layer according to claim 2 in an organic photoelectric device.

4. An organic optoelectronic device, comprising one or more of the compounds according to claim 1 or the organic layer according to claim 2.

5. The organic optoelectronic device according to claim 4, characterized in that: It comprises a substrate, a first electrode, an organic layer and a second electrode, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer, and its material comprises one or more of the compounds described in claim 1.

6. A display or lighting device, characterized in that: Comprising the organic photoelectric device according to claim 4 or 5.

Images