Organic compounds and their applications, organic electroluminescent devices

Abstract

The present invention provides a compound and its application. The compound has a structure shown in Formula 1-1. When the compound of the present invention is used in an organic electroluminescent device, especially as an electron injection / transport material, the device excitation voltage can be effectively reduced, the device luminous efficiency can be improved, and the best effect can be achieved.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, in particular to an organic compound and application thereof, and also to an organic electroluminescence device. Background Art

[0002] In recent years, organic light-emitting diodes (OLEDs) have developed rapidly and have a place in the field of information display. This is mainly due to the fact that OLED devices can use high-saturation red, green and blue primary colors to prepare full-color display devices, and can achieve colorful, light, thin and soft performance without the need for additional backlight sources. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, etc. The core of OLED devices is a thin film structure containing a variety of organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guests (dyes), etc.

[0003] In order to prepare OLED light-emitting devices with lower driving voltage, better luminous efficiency and longer device life, and to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously study and innovate the optoelectronic functional materials in OLED devices to prepare functional materials with higher performance. Based on this, the OLED material industry has been committed to developing new organic electroluminescent materials to achieve low device starting voltage, high luminous efficiency and better device life.

[0004] In recent years, OLED displays are increasingly used in mobile phones, portable tablets, as well as wearable devices such as watches, glasses, VR devices, etc. These devices are mostly powered by batteries. If the display can achieve higher luminous efficiency with lower voltage and current, it will undoubtedly mean that the overall portable device will be lighter and have longer battery life. Therefore, higher requirements are put forward for reducing the excitation power of OLED devices and increasing luminous efficiency. It is difficult for the industry to reduce the driving voltage on the existing basis. Even a reduction of 0.1V under the same conditions of luminous performance is a huge improvement in performance, which will make the final device product significantly lighter or have longer power endurance, and therefore have stronger market competitiveness.

[0005] At present, OLED screen manufacturers widely use the technical means of doping Liq (lithium octahydroxyquinoline) into the electron transport material layer to achieve low voltage and high efficiency of the device, and to improve the life of the device. The main role of Liq is to reduce a trace amount of metallic lithium under the action of electrons injected by the cathode, thereby playing the role of n-doping the electron transport material, thereby significantly improving the electron injection effect. On the other hand, lithium ions will improve the electron mobility of the ET material through coordination with the N atoms in the electron transport material, so that the Liq-doped ET device has a low operating voltage and high luminous efficiency.

[0006] Patent Document 1 discloses an electron transporting compound doped with Liq.

[0007]

[0008] Patent document 1: WO2010062065A2

[0009] However, the inventors found that the luminous performance was still not ideal when they studied it. In order to further meet the demand for the continuous improvement of the optoelectronic performance of OLED devices and the demand for energy saving in mobile electronic devices, it is necessary to continuously develop new and efficient OLED materials, among which the development of new electron transport materials with high electron injection ability and high mobility is of great significance. Summary of the invention

[0010] The purpose of the present invention is to provide an organic compound, which can be used as an organic functional material in an organic electroluminescent device to effectively reduce the driving voltage and improve the luminous efficiency of the device. To achieve this purpose, the inventors have devoted themselves to research and developed the following organic compounds to complete the present invention

[0011] Specifically, the present invention provides an organic compound having a structure shown in Formula 1-1;

[0012]

[0013] Among them, X 1 ~X 5 CH or N, where the H of CH can be replaced by R 2 or R 3 Replace; Y 1 ~Y 3 CH or N, where the H of CH can be replaced by R 4 Replace, Y 1 ~Y 3 At least one of is N;

[0014] L is selected from a single bond, a substituted or unsubstituted C6-C30 Arylene or substituted or unsubstituted C3~C 30 heteroarylene;

[0015] R 1 ~R 4 are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3~C 30 Heteroaryl, C1~C 30 Alkyl, C1~C 30 Alkoxy, C7~C 30 Arylalkoxy, C3~C 30 Cycloalkyl, C2~C 30 Alkenyl, C2~C 30 m is an integer of 0 to 4, n is an integer of 0 to 3, p is an integer of 0 to 4, preferably p is an integer of 0 to 3, q ​​is an integer of 0 to 5, preferably q is an integer of 0 to 3, and multiple R 1 When they are the same or different, multiple R 1 They are not connected to each other and are multiple R 2 When they are the same or different, multiple R 2 They are not connected to each other and are multiple R 3 When they are the same or different, multiple R 3 They are not connected to each other and are multiple R 4 When they are the same or different, in view of the ease of synthesis and the availability of raw materials, R 1 ~R 4 All are single-bonded to the parent nucleus.

[0016] When the above substituted or unsubstituted groups have substituents, the substituents are selected from halogen, C1-C 30 Alkyl, C3~C 30 Cycloalkyl, C2~C 30 Alkenyl, C1~C 30 Alkoxy or thioalkoxy, cyano, nitro, C1~C 30 Amine, carboxyl, aldehyde, ester, C6~C 30 Aryl, C3~C 30 A combination of one or more heteroaryl groups.

[0017] The inventors have found that when the above-mentioned compound of the present invention is used in combination with Liq in the electron transport layer or electron injection layer of an organic electroluminescent device, the device can achieve low driving voltage and high device luminous efficiency. The specific reasons for achieving these excellent technical effects are not clear, and the following are the inventors' speculations, but these speculations do not limit the scope of protection of the present invention.

[0018] The parent core structure of the compound of the present invention adopts the structure of benzimidazole phenanthrene, has good affinity to electrons, and has a relatively larger planar structure, improves the electron migration ability, thereby is conducive to improving the mobility of the electrons of the newly constructed molecule as a whole. The structural characteristics of the above two aspects can make the molecule as a whole show good electron injection and migration performance. More importantly, in the present invention, via the L group, some aromatic groups containing N atoms are connected on the phenanthrene side of benzimidazole phenanthrene, compared to the prior art, it is more conducive to the injection of electrons and the ability of transmission to reach a balance, avoid the excessive electron injection ability and the electron enrichment in the inside of the molecular structure but reduce the efficiency of the device.

[0019] In the compound of the present invention, R 1 ~R 3 It is connected to the parent nucleus by a single bond and is not fused with the parent nucleus, which can ensure the planar structure of the parent nucleus and ensure a good channel for carrier flow.

[0020] The above compounds of the present invention have basically achieved a good effect of reducing the excitation voltage compared to the prior art. Furthermore, the present inventors have found that if the compound of formula 1-1 is a compound represented by the following general formula 2-1 or 2-2, it can further greatly reduce the excitation power supply and improve the luminous efficiency.

[0021]

[0022] X 1 ~X 4 , Y 1 ~Y 3 , L and q have the same meanings as those in Formula 1-1, where R 1 ~R 4 are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C6-C 18 Aryl, substituted or unsubstituted C3~C 18 Heteroaryl, C1~C 12 alkyl.

[0023] The specific reasons why the compounds of formula 2-1 or 2-2 can further achieve excellent technical effects are not yet clear. The following are speculations of the inventors, but these speculations do not limit the scope of protection of the present invention.

[0024] For the benzimidazole phenanthrene group structure in which N is added to the parent core on the basis of benzimidazole phenanthrene, and N is located near the ring, that is, the following structure, compared with benzimidazole phenanthrene, it has a stronger affinity for electrons and therefore has a stronger electron-withdrawing ability.

[0025]

[0026] In addition, the inventors found that when the N substitution of phenanthroline is located at other positions, the effect is not as good as the state where N is located close to the ring (as shown in the above formula). This shows that the location of N of phenanthroline close to the ring is also very important. It is speculated that this may make the parent core more conducive to the balance of the electron cloud, thereby reducing the device driving voltage and efficiency.

[0027] It should be noted that in this manual, C a ~C b The expression "a" means that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms in the substituent. In the present invention, the expression of chemical elements, unless otherwise specified, generally includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen" also includes the concept of "deuterium" and "tritium" with the same chemical properties. Carbon (C) includes 12 C. 13 C, etc., no further details.

[0028] In the structural formula disclosed in this specification, the expression of the ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0029] In this specification, unless otherwise specified, aryl and heteroaryl include both monocyclic and condensed rings. The so-called monocyclic aryl refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, biphenyl, terphenyl, etc.; condensed ring aryl refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but condensed to each other by sharing the ring edge, such as naphthyl, anthracenyl, etc.; monocyclic heteroaryl refers to a molecule containing at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and connected by a single bond, such as pyridine, furan, thiophene, etc.; condensed ring heteroaryl refers to a molecule composed of at least one phenyl group and at least one heteroaryl group fused together, or at least two heteroaryl rings fused together, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc.

[0030] In this specification, substituted or unsubstituted C6 to C 30 The aryl group is preferably C6-C 20The aryl group is more preferably a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenylene, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aryl group in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9, 9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, The naphthacene group is selected from the group consisting of 1-naphthacene, 2-naphthacene and 9-naphthacene.

[0031] Specific examples of the arylene group in the present invention include divalent groups obtained by removing one hydrogen atom from the above-mentioned aryl groups.

[0032] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0033] In this specification, substituted or unsubstituted C3 to C 30 The heteroaryl group is preferably C4 to C 20The heteroaryl group is more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like. Specific examples thereof include a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an isobenzothienyl group, an indolyl group, an isoindolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and its derivatives, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo-5,6-quinolyl group, a benzo-6,7-quinolyl group, a benzo-7,8-quinolyl group, a phenothiazinyl group, a phenazinyl group, a pyrazolyl group, an indazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthoimidazolyl group, a phenanthroimidazolyl group, a pyridoimidazolyl group, a pyrazinoimidazolyl group, a quinoxalinoimidazolyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, an anthrazolyl group, a phenanthroxazolyl group, a 1, 2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole and the like. Preferred examples of heteroaryl groups in the present invention include furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole or indolecarbazole.

[0034] Specific examples of the heteroarylene group in the present invention include divalent groups obtained by removing one hydrogen atom from the above-mentioned heteroaryl groups.

[0035] The aryloxy group in the present invention includes a monovalent group composed of the above-mentioned aryl group and heteroaryl group and oxygen.

[0036] In this specification, C1 to C 30Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, adamantyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, and 2,2,2-trifluoroethyl.

[0037] In this manual, C3 to C 30 The cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

[0038] In this specification, C1 to C 30 Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy, and methoxy is more preferred.

[0039] In this specification, C2 to C 30 Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, etc.; 30 Examples of the alkynyl group include ethynyl, propynyl, and 1-butynyl.

[0040] In this specification, C1 to C 30 Examples of the silane group may be 30 Specific examples of the silyl group substituted with the groups listed above for the alkyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like.

[0041] In the present specification, examples of halogen include fluorine, chlorine, bromine, and iodine.

[0042] More specifically, as the above-mentioned R 1 ~R 4The group preferably includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, naphthacene, pentacene, benzopyrene, biphenyl, phenylene, terphenyl, triphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, triindenyl, isotriindenyl, spirotriindenyl, spiroisotriindenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8- quinolinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalin imidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4, 5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, One of 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, or a combination of two of the above groups.

[0043] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the present invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0044] In the present invention, L is preferably a single bond or a group selected from phenylene, naphthylene, biphenylene, pyridylene, anthracene or a divalent group formed by a combination of these groups, and these groups may have a substituent, and the substituent is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, cyano, nitro, C6-C 18 Aryl, C3~C 18 A combination of one or more of the heteroaryl groups.

[0045] In the above formula 1, formula 2-1, and formula 2-2, preferably X 1 ~X 4 All are CH, or X 1 ~X 4 In the case where one of them is N and the other three are CH, the number of N in the parent core is just right, the affinity for electrons is appropriate, and it is particularly suitable for use as a material for the electron transport / injection layer.

[0046] In the above formula 1, formula 2-1, and formula 2-2, R 1 ~R 3 are independently selected from H, halogen, cyano, C1-C6 alkyl, C6-C 18 Aryl, C3~C 18 A combination of one or more heteroaryl groups, wherein H, halogen, cyano, methyl, ethyl, propyl, isopropyl, cyclohexyl, phenyl, pyridyl, naphthyl, benzofuranyl, fluorenyl are preferred, and halogen is preferably fluorine atom or chlorine atom, R 1 ~R 3 In the above formula 1, formula 2-1 and formula 2-2, R 4 Each independently preferably is selected from C6 to C 18 Aryl, C3~C 18 A combination of one or more heteroaryl groups, q is preferably an integer of 1 to 3, R 4 More preferred are phenyl, pyridyl, naphthyl, benzofuranyl and fluorenyl.

[0047] Preferred Y 1 ~Y 3 Two or more of them are N atoms, more preferably Y 1 ~Y 3 All are N atoms.

[0048] From the viewpoint of the better electron transport property of the compound of the present invention, a more preferred composition is one in which L is a phenylene group or a single bond, and Y is 1 ~Y 3 are all N atoms, q is 2, R 4 It is phenyl.

[0049] Furthermore, the organic compound of the present invention can preferably include the specific structural compounds shown in the following A1 to A131. These compounds are only representative and do not limit the scope of the present invention.

[0050]

[0051]

[0052]

[0053]

[0054] .

[0055] In addition, the preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, it is suitable for mass production and expansion, and is very suitable for industrial application.

[0056] The above-mentioned compound of the present invention has a high electron affinity and thus has a strong ability to absorb electrons. Based on its excellent electron transport and electron injection effects, it is suitable for use as an electron transport material, and is particularly suitable for use as an electron transport / injection material. However, the application scenarios of the compound of the present invention are not limited to electron blocking materials, and can also be used as hole blocking materials, host materials, etc. for organic electronic devices. Such organic electronic devices include, but are not limited to, organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic paper, preferably organic electroluminescent devices.

[0057] The present invention also provides an organic electroluminescent device, which comprises a first electrode, a second electrode and at least one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer contains at least one compound described in the present invention.

[0058] The organic electroluminescent device of the present invention has a structure consistent with that of existing devices, for example, comprising an anode layer, multiple light-emitting functional layers and a cathode layer; the multiple light-emitting functional layers include a light-emitting layer and at least one layer selected from an electron transport layer and an electron injection layer, wherein at least one layer selected from the electron transport layer, the electron injection layer or the hole blocking layer contains the above-mentioned organic compound of the present invention.

[0059] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is further described in more detail below. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0061] Method for obtaining the compound of the present invention

[0062] The compound represented by the general formula 1-1 of the present invention can be obtained by a known method, for example, by a known organic synthesis method. An exemplary synthesis route is given below, but those skilled in the art can also obtain it by other known methods.

[0063]

[0064] The structure of the organic electroluminescent device of the present invention is a well-known structure, and the compound of the present invention is used in the electron transport layer and / or the electron injection layer. The organic electroluminescent device is described in detail below.

[0065] OLED includes a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0066] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0067] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0068] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0069] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0070] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0071]

[0072]

[0073]

[0074]

[0075] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-51 above, or one or more compounds of HI1-HI3 below; or one or more compounds of HT-1 to HT-51 can be doped with one or more compounds of HI1-HI3 below.

[0076]

[0077] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0078] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0079] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0080]

[0081] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFD-1 to BFD-24 listed below.

[0082]

[0083]

[0084] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology, and the main material of the light-emitting layer is selected from, but not limited to, one or more combinations of PH-1 to PH-85.

[0085]

[0086]

[0087]

[0088]

[0089] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0090]

[0091]

[0092] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0093]

[0094]

[0095] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0096]

[0097] In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence luminescence. The main material of the light-emitting layer is selected from, but not limited to, one or more combinations of the above PH-1 to PH-85.

[0098] In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but not limited to, one or more of the compounds HT-1 to HT-51 described above, or one or more of the compounds PH-47 to PH-77 described above; or a mixture of, but not limited to, one or more of the compounds HT-1 to HT-51 and one or more of the compounds PH-47 to PH-77.

[0099] The organic EL light-emitting device of the present invention includes an electron transport region between a light-emitting layer and a cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0100] The electron transport region can also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL) using the above-mentioned compound of the present invention. Of course, the material of the electron transport region can also be a combination of one or more of ET-1 to ET-65 listed below, typically used in combination with Liq (ET-57 described below).

[0101]

[0102]

[0103]

[0104] In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may be, but not limited to, one or more compounds of ET-1 to ET-65, or one or more compounds of PH-1 to PH-46; or a mixture of, but not limited to, one or more compounds of ET-1 to ET-65 and one or more compounds of PH-1 to PH-46.

[0105] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes, but is not limited to, one or more combinations of the following:

[0106] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg.

[0107] Example

[0108] The organic compounds of the present invention were synthesized representatively, and applied together with corresponding comparative compounds in organic electroluminescent devices to test the device performance under the same conditions.

[0109] The following synthesis examples of the present invention illustratively provide specific synthesis methods of representative compounds. The solvents and reagents, intermediates, ethyl acetate, methanol, ethanol and other chemical reagents used in the following synthesis examples can all be purchased or customized from the domestic chemical product market, for example, purchased from Sinopharm Group Reagent Company, Sigma-Aldrich Company, and J&K Reagent Company.

[0110] Synthesis Example

[0111] Synthesis Example 1:

[0112] Synthesis of Compound A1

[0113]

[0114] Preparation of compound A1-1

[0115] M1 (24.3 g, 100 mmol), 2-(2-fluoropyridine)-4-chlorophenylboronic acid (25.1 g, 120 mmol), potassium carbonate (41.4 g, 300 mmol), 280 mL toluene, 40 mL ethanol, and 40 mL water were added to a 500 mL three-necked flask. After nitrogen replacement three times, Pd(PPh3)4 (1.1 g, 1 mmol) was added, and then heated to 110°C for 5 h. TLC showed that the reaction was complete. Toluene and ethanol were concentrated, and an appropriate amount of water was added and extracted with DCM. The organic phase was collected, concentrated, and silica gel was added to mix the sample. Silica gel column chromatography was used to separate 25.8 g of compound A1-1.

[0116] Preparation of Compound A1-2

[0117] Take the prepared compound A1-1 (25.8g, 80mmol) and dissolve it in 250mL DMF in a 500mL three-necked flask, cool it down to 0°C under nitrogen protection, slowly add sodium hydride (2.3g, 96mmol) in batches, stir at room temperature for one hour after addition, and then heat to 100°C overnight. TLC shows that the reaction is complete. Cool to room temperature, add 500mL of water, and extract three times with 1000mL of ethyl acetate, combine the organic phases and extract once with 200mL of saturated brine. Collect the concentrated organic phase, add silica gel and stir, and separate by silica gel column chromatography to obtain 13.5g of compound A1-2.

[0118] Preparation of Compound A1

[0119] A1-2 (13.5 g, 44 mmol), 2-(3-boric acid ester) phenyl-4, 6-diphenyl-1,3,5-triazine (22.9 g, 52 mmol), potassium carbonate (16.9 g, 123 mmol), 150 mL of dioxane and 20 mL of water were added to a 250 mL three-necked flask. After nitrogen replacement three times, Pd2(dba)3 (0.4 g, 0.44 mmol) and Sphos (0.36 g, 0.88 mmol) were added, and then heated to 110 ° C for 7 hours. A large amount of solid precipitated from the system, and TLC showed that the reaction was complete. Cool to room temperature, filter and rinse with 200 mL of ethanol three times, dry and then heat with 2 L of toluene to reflux and dissolve, filter with a short silica gel column while hot and perform column chromatography separation, collect and concentrate to obtain 13.4 g of white powder A1.

[0120] The molecular weight of the white powder was measured by mass spectrometer (ZAB-HS mass spectrometer, manufactured by Micromass, UK), instrument conditions: direct injection, EI source, ionization voltage 70 eV, ionization temperature 250°C, acceleration voltage 6 kV, resolution 1000. The calculated molecular weight value: 576.21, the measured value C / Z: 576.2, and it was confirmed to be the target compound A1 according to the synthesis route. The following method for determining the structure of the compound in the present invention is similar to this.

[0121] Synthesis Example 2:

[0122] Synthesis of Compound A7

[0123]

[0124] Preparation of Compound A7

[0125] Take the compound A1-2 (15.1 g, 50 mmol) prepared in Synthesis Example 1 and add it to a three-necked flask, then add 2-(3-methyl-4-boric acid ester) phenyl-4,6-diphenyl-pyrimidine (26.8 g, 60 mmol), potassium carbonate (20.7 g, 150 mmol), and then add 150 mL of dioxane and 20 mL of water. After nitrogen replacement three times, add Pd2(dba)3 (0.45 g, 0.5 mmol) and Sphos (0.41 g, 1 mmol), then heat to 110 ° C for 6 hours, a large amount of solid precipitates in the system, and TLC shows that the reaction is complete. Cool to room temperature, filter and rinse with 300 mL of ethanol three times, dry and then heat with 1 L of xylene to reflux and dissolve, separate by hot silica gel column chromatography, collect and concentrate to obtain 16.7 g of white powder A7. Molecular weight calculation value: 589.23, measured value C / Z: 589.2.

[0126] Synthesis Example 3:

[0127] Synthesis of compound A21

[0128]

[0129] According to the synthesis method in Synthesis Example 1, except that M1 is replaced by M2 in the preparation of intermediate A21-1, intermediate A21-1 is obtained; and in the preparation of final product A21, 2-(3-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine is replaced by 4,6-dipyridyl-2-pyridine boronic acid to obtain 8.5 g of A21. The calculated molecular weight is 576.21, and the measured C / Z is 576.2.

[0130] Synthesis Example 4:

[0131] Synthesis of Compound A41

[0132]

[0133] Preparation of Compound A41

[0134] The synthesis method in Synthesis Example 1 was followed, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid was replaced by 3-(2-fluoropyridyl)-6-chloro-2-pyridineboronic acid in the preparation of intermediate A41-1. The syntheses of intermediate A41-2 and final product A41 were both prepared according to the method in Synthesis Example 1 to obtain 12.11 g of A41 with a calculated molecular weight of 577.23 and a measured C / Z of 577.2.

[0135] Synthesis Example 5:

[0136] Synthesis of compound A50

[0137]

[0138] Preparation of compound A50-1

[0139] M3 (26.8 g, 100 mmol), 3-(2-fluoropyridyl)-6-chloro-2-pyridineboronic acid (30.24 g, 120 mmol), potassium carbonate (41.4 g, 300 mmol), 300 mL toluene, 50 mL ethanol, and 50 mL water were added to a 500 mL three-necked flask. After nitrogen replacement three times, Pd(PPh3)4 (1.1 g, 1 mmol) was added, and then heated to 110°C for 5 h. TLC showed that the reaction was complete. Toluene and ethanol were concentrated, 280 mL of water was added, and the mixture was extracted with 900 mL of DCM. The organic phase was collected, concentrated, and silica gel was added to mix the sample. 29.3 g of compound A50-1 was obtained by silica gel column chromatography.

[0140] Preparation of compound A50-2

[0141] The compound A50-1 (29.3 g, 84 mmol) obtained in the previous step was dissolved in 300 mL DMF and placed in a 500 mL three-necked flask, cooled to 0 ° C under nitrogen protection, and sodium hydride (3.0 g, 126 mmol) was slowly added in batches. After the addition, it was stirred at room temperature for one hour, and then the temperature was raised to 130 ° C for reaction for 14 h. TLC detection showed that the reaction was complete. Cool to room temperature, add 500 mL of water, and extract three times with 1200 mL of ethyl acetate, combine the organic phases and extract once with 300 mL of saturated brine. Collect the concentrated organic phase, add silica gel and stir, and separate by silica gel column chromatography to obtain 14.0 g of compound A50-2.

[0142] Preparation of compound A50

[0143] A50-2 (14 g, 42 mmol), 2-(3-boric acid ester) phenyl-4, 6-diphenyl-1,3,5-triazine (21.92 g, 50 mmol), potassium carbonate (17.4 g, 126 mmol), 150 mL of dioxane and 20 mL of water were added to a 250 mL three-necked flask. After nitrogen replacement three times, Pd2(dba)3 (0.37 g, 0.4 mmol) and Sphos (0.32 g, 0.8 mmol) were added, and then heated to 110 ° C for 9 h. A large amount of white solid precipitated from the system, and TLC showed that the reaction was complete. Cool to room temperature, filter and rinse with 300 mL of ethanol three times, dry and then heat with 3 L of toluene to reflux to dissolve, remove palladium by filtering with a short silica gel column while hot, collect and cool and stand to precipitate a white solid, filter and dry to obtain 12.6 g of white solid A50. Calculated molecular weight: 602.20, measured C / Z: 602.2.

[0144] Synthesis Example 6:

[0145] Synthesis of compound A104

[0146]

[0147] According to the synthesis method in Synthesis Example 1, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid is replaced by 3(2-fluoro-4-chloro)pyridyl-2-phenylboronic acid in the preparation of intermediate A104-1, A104-1 is obtained; in addition, except that 2-(3-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine is replaced by 2-(3-boric acid ester-5-phenyl)phenyl-4,6-diphenyl-1,3, 5-triazine 4,6-diphenyl-2-(5-boric acid ester-[1,1'-biphenyl]-3-yl)pyrimidine in the preparation of final product A104, A104 10g is obtained. Molecular weight calculated value: 651.24, measured value C / Z: 651.2.

[0148] Synthesis Example 7

[0149] Synthesis of Compound A106

[0150]

[0151] According to the synthesis method in Synthesis Example 1, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid was replaced by 3(2-fluoro-5-chloro)pyridyl-2-phenylboronic acid in the preparation of intermediate A106-1, A106-1 was obtained; in addition, the synthesis of intermediate A106-2 and final product A106 was carried out according to the method in Synthesis Example 1 to obtain 8 g of white solid A106. The calculated molecular weight was 576.21, and the measured C / Z was 576.2.

[0152] Synthesis Example 8

[0153] Synthesis of Compound A107

[0154]

[0155] The synthesis method of Synthesis Example 7 was followed, except that 2-(3-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine was replaced by 2-(4-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine to obtain 10.5 g of A107 with a calculated molecular weight of 576.21 and a measured C / Z of 576.2.

[0156] Synthesis Example 9

[0157] Synthesis of compound A121

[0158]

[0159] A106-2 (10 g, 33 mmol) synthesized according to the preparation method in Synthesis Example 7 was added to a three-necked flask, and then 2-boric acid ester-6-(3-spiro[cyclohexane-1,9-dimethylfluorene]) pyridine (17.3 g, 40 mmol), potassium carbonate (20.7 g, 150 mmol), and then 140 mL of dioxane and 23 mL of water were added. After nitrogen replacement three times, Pd2(dba)3 (0.45 g, 0.5 mmol) and Sphos (0.41 g, 1 mmol) were added, and then heated to 112 ° C for 8 h. A large amount of solid precipitated from the system, and TLC showed that the reaction was complete. Cool to room temperature, filter and rinse with 200 mL of ethanol three times, dry and then dissolve with 2 L of DCM, separate by silica gel column chromatography, collect and concentrate to obtain 10.6 g of white powder A121. Calculated molecular weight: 578.25, measured C / Z: 578.2.

[0160] Synthesis Example 10

[0161] Synthesis of Compound A123

[0162]

[0163] According to the synthesis method in Synthesis Example 1, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid is replaced by 4-[3-(2-fluoro-4-chloro)pyridyl]-3-pyridineboronic acid in the preparation of intermediate A123-1, A123-1 is obtained; in addition, except that 2-(3-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine is replaced by 4-(4-boric acid ester)phenyl-2,6-diphenyl-pyridine in the preparation of final product A123, 9.6 g of white solid A123 is obtained. Calculated molecular weight: 575.24, measured C / Z: 575.2.

[0164] Synthesis Example 11

[0165] Synthesis of Compound A125

[0166]

[0167] Preparation of compound A125-1

[0168] M4 (19.6 g, 100 mmol) was added to a 500 mL three-necked flask, dissolved in 200 mL DMF, and then 2-iodo-3-chloro-4-hydroxypyridine (25.4 g, 100 mmol), potassium carbonate (41.4 g, 300 mmol), CuI (3.8 g, 20 mmol), and 1,10-phenanthroline (7.2 g, 40 mmol) were added. After nitrogen replacement three times, the mixture was heated to 150 ° C and reacted for 10 h. M4 disappeared after TLC detection, and the heating was stopped and cooled to room temperature. 400 mL of water was added and extracted with 600 mL of ethyl acetate. The organic phase was collected, concentrated, and silica gel was added to mix the sample. 22.9 g of compound A125-1 was obtained by silica gel column chromatography.

[0169] Preparation of compound A125-2

[0170] A125-1 (22.9 g, 71 mmol), 2-fluorophenylboronic acid (12 g, 85 mmol), potassium carbonate (29.3 g, 213 mmol) were added to a 500 mL three-necked flask, and then 230 mL of THF and 40 mL of water were added. After nitrogen replacement three times, Pd(PPh3)4 (0.8 g, 0.7 mmol) was added, and then heated to 80 ° C for 6 h. TLC showed that the reaction was complete. Cooled to room temperature, 80 mL of water was added, and then extracted with 500 mL of DCM three times, the concentrated organic phase was collected, and column chromatography was used to separate 21.4 g of A125-2.

[0171] Preparation of compound A125-3

[0172] A125-2 (21.4 g, 63 mmol) obtained in the previous step was added to a 500 mL three-necked flask, potassium carbonate (26 g, 189 mmol), palladium acetate (2.8 g, 12 mmol) and tri-tert-butylphosphine tetrafluoroborate (6.9 g, 24 mmol), and then 200 mL of N, N-dimethylacetamide was added and heated to 160°C under nitrogen protection for 18 h. After cooling to room temperature, 400 mL of water was added and then extracted three times with 800 mL of ethyl acetate, the organic phase was washed once with 200 mL of saturated brine, the organic phase was collected and concentrated, and column chromatography was used to obtain 8 g of A125-3.

[0173] Preparation of Compound A125-4

[0174] A125-3 (8 g, 26 mmol) was added to a 250 mL three-necked flask, dissolved in 80 mL of DCM, and then triethylamine (4 g, 40 mmol) was added and stirred in an ice bath, and trifluoromethanesulfonic anhydride (8.8 g, 31 mmol) was slowly added dropwise. After the addition was completed, the reaction was allowed to react at room temperature for 8 h. After TLC detection, 50 mL was added to quench the reaction, and then 50 mL of DCM was added to extract and collect the organic phase, and column chromatography was used to separate 8.6 g of A125-4.

[0175] Preparation of Compound A125

[0176] A125-4 (8.6 g, 20 mmol), 2-3 (3-boronic acid ester-biphenyl) -3-yl-4,6-diphenylpyrimidine 2-(3-(10.1 g, 20 mmol), potassium phosphate (12.7 g, 60 mmol) were added to a 250 mL three-necked flask, and then 100 mL of dioxane was added. After nitrogen replacement three times, Pd (dppf) 2Cl 2 (0.29 g, 0.4 mmol) was added, and then heated to 110 ° C for 8 h. A large amount of white solid precipitated from the system, and TLC showed that the reaction was complete. Cool to room temperature, filter and rinse three times with 125 mL of ethanol, dry and then heat with 1400 mL of xylene to reflux and dissolve. Filter and remove palladium with a silica gel short column while hot. After collection, cool and stand, a white solid precipitates, which is filtered and dried to obtain a white solid A125 5.5 g. Calculated molecular weight: 669.23, measured C / Z: 669.2. Synthesis Example 12

[0177] Synthesis of Compound A129

[0178]

[0179] A129-1 was synthesized according to the synthesis method in Synthesis Example 1, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid was replaced by (5-chloro-2-fluoro-[1,1'biphenyl]-2-yl)boric acid. A129-2 was synthesized according to the synthesis method in Synthesis Example 1, and then 2-(3-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine was replaced by 2-(4-boric acid ester)phenyl-4,6-diphenyl-1,3,5-triazine. According to the method in Example 1, A129 11.3 g was synthesized, with a calculated molecular weight of 575.21 and a measured C / Z of 575.2.

[0180] Synthesis Example 13

[0181] Synthesis of compound A130

[0182]

[0183] Preparation of compound A130-2

[0184] The synthesis method of Synthesis Example 1 was followed, except that 2-(2-fluoropyridine)-4-chlorophenylboronic acid was replaced with [2-(5-chloro-2-fluorophenyl)pyridin-3-yl]boronic acid to obtain 12.6 g of A130-2.

[0185] Preparation of compound A130-3

[0186] A130-2 (12.6 g, 41 mmol), biboronic acid pinacol ester (15.6 g, 61 mmol), potassium acetate (12.0 g, 123 mmol) and Pd(dppf)2Cl2 (1.5 g, 2 mmol) were added to a 250 mL three-necked flask and dissolved in 150 mL of dioxane. Under nitrogen protection, the temperature was raised to 120 ° C and refluxed for 11 hours. After TLC detection, the reaction was completed, the solvent was concentrated, 200 mL of dichloromethane was added to dissolve and filter out the inorganic salt, and the filtrate was separated by column chromatography to obtain 13.2 g of A130-3.

[0187] Preparation of compound A130

[0188] A130-3 (13.2 g, 33 mmol), 2-chloro-4,6-diphenyl-1,3,5 triazine (8.8 g, 33 mmol), potassium phosphate (13.6 g, 99 mmol) were added to a 250 mL three-necked flask, and then 150 mL of dioxane and 20 mL of water were added. After nitrogen replacement three times, Pd(dppf)2Cl2 (0.76 g, 1 mmol) was added, and then heated to 110 ° C for 8 h. A large amount of white solid precipitated from the system, and TLC showed that the reaction was complete. Cool to room temperature, filter and rinse with 130 mL of ethanol three times, dry and then heat with 1800 mL of toluene to reflux to dissolve, filter and remove palladium with a silica gel short column while hot, collect and cool and stand to precipitate a white solid, filter and dry to obtain 8.4 g of white solid A130. Molecular weight calculation value: 500.17, measured value C / Z: 500.1.

[0189] Synthesis Example 14

[0190] Synthesis of Compound A131

[0191]

[0192] The synthesis method in Synthesis Example 13 was followed, except that [2-(5-chloro-2-fluorophenyl)pyridin-3-yl]boric acid was replaced with (5-chloro-2-fluoro-[1,1'biphenyl]-2-yl)boric acid to obtain 9.5 g of A131 with a calculated molecular weight of 499.18 and a measured C / Z of 499.1.

[0193] Comparative Synthesis Example 1

[0194] Synthesis of compound E1

[0195]

[0196] The synthesis method in Synthesis Example 13 was followed, except that M1 was replaced by M5, and [2-(5-chloro-2-fluorophenyl)pyridin-3-yl]boric acid was replaced by (2'-fluoro-[1,1'biphenyl]-2-yl)boric acid to obtain E1 8.7 g, with a calculated molecular weight of 499.18 and a measured C / Z of 499.1.

[0197] Comparative Synthesis Example 2

[0198] Synthesis of compound E2

[0199]

[0200] The synthesis method in Synthesis Example 1 was followed, except that [2-(5-chloro-2-fluorophenyl)pyridin-3-yl]boric acid was replaced with [5-fluoro-2-(4-fluoropyridin-3-yl]phenylboric acid in the first intermediate synthesis to obtain E2 6.8 g, with a calculated molecular weight of 576.21 and a measured C / Z of 576.2.

[0201] Device Embodiment

[0202] The organic electroluminescent device preparation process in the device embodiment of the present invention is as follows:

[0203] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0204] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a pressure less than 10 -5 Pa, vacuum-deposit 10 nm of HI-3 on the above anode layer as a hole injection layer;

[0205] Vacuum evaporate 40 nm of HT-4 on the hole injection layer as the first hole transport layer of the device;

[0206] Vacuum evaporate 5 nm of HT-14 on the first hole transport layer as the second hole transport layer of the device;

[0207] Vacuum-deposit a 20 nm light-emitting layer of the device on the second hole transport layer, wherein the light-emitting layer includes a main material BFH-4 and a dye material BFD-4;

[0208] 5 nm of ET-17 was vacuum-evaporated on the light-emitting layer as the hole blocking layer of the device;

[0209] On the hole blocking layer, a representative compound of the electron transport material A1 to A131 of the present invention or a comparative material E1-E2 is vacuum-evaporated by a multi-source co-evaporation method, and the evaporation rate of ET-57 is set at 100%, and the total film thickness of the evaporation is 23 nm;

[0210] LiF with a thickness of 1 nm was vacuum-deposited on the electron transport layer (ETL) as the electron injection layer, and an aluminum layer with a thickness of 80 nm was used as the cathode of the device. The evaporation rate of all organic layers and LiF was 0.1 nm / s, and the evaporation rate of metal aluminum was 1 nm / s.

[0211] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0212] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1 to 10 and Comparative Examples 1-2 were measured. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage when the brightness of the organic electroluminescent device reached 1000 cd / m2, i.e., the driving voltage, was measured, and the current density at this time was measured; the ratio of the brightness to the current density was the current efficiency;

[0213] Example 1

[0214] The compound A1 of the present invention is used as an electron transport material, an organic electroluminescent device is prepared according to the above-mentioned preparation process of the organic electroluminescent device, and the device performance is tested according to the above-mentioned test method for the organic electroluminescent device.

[0215] Example 2

[0216] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A7.

[0217] Example 3

[0218] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A21.

[0219] Example 4

[0220] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A41.

[0221] Example 5

[0222] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A50.

[0223] Example 6

[0224] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A104.

[0225] Example 7

[0226] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A106.

[0227] Example 8

[0228] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A107.

[0229] Example 9

[0230] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A121.

[0231] Example 10

[0232] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A123.

[0233] Embodiment 11

[0234] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A125.

[0235] Embodiment 12:

[0236] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A129.

[0237] Embodiment 13:

[0238] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A130.

[0239] Embodiment 14:

[0240] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by A131.

[0241] Comparative Example 1:

[0242] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by E1.

[0243] Comparative Example 2:

[0244] An organic electroluminescent device was prepared by the same method as in Example 1, except that compound A1 was replaced by E2.

[0245] Table 1:

[0246]

[0247] The above experimental data show that the novel organic material of the present invention, as an electron blocking material for an organic electroluminescent device, has been significantly improved compared with the prior art, is an organic light-emitting functional material with good performance, and has broad application prospects.

[0248] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic compound, characterized in that is a compound represented by the following general formula 2-1 or 2-2, Among them, X 1 ~X 4 CH or N; Y 1 ~Y 3 is CH or N, where the H of CH is replaced by R 4 Replace or not replace, Y 1 ~Y 3 At least one of is N; L represents a single bond, or represents a group selected from phenylene, naphthylene, biphenylene, pyridylene, and anthracene; R 1 is hydrogen, halogen, cyano, phenyl, biphenyl, naphthyl, furyl, thienyl, pyrrolyl, pyridyl, or C1-C 12 Alkyl; R 2 is hydrogen; R 3 is hydrogen; R 4 Each independently selected from C6 to C 18 Aryl, C3~C 18 q is an integer of 1 to 3, which is a combination of one or more heteroaryl groups of R 4 , they are the same or different.

2. The organic compound according to claim 1, wherein X 1 ~X 4 All are CH, or X 1 ~X 4 One of them is N, and the other three are CH. Y 1 ~Y 3 Two or more of them are N atoms.

3. The organic compound according to claim 1, wherein R 1 ~R 3 is hydrogen, Y 1 ~Y 3 All are N atoms.

4. The organic compound according to claim 1 is a compound having the following specific structure: 5 . An electron transport / injection material, which is the compound according to claim 1 .

6. Use of the compound according to any one of claims 1 to 4 as a functional material in an organic electronic device, wherein the organic electronic device comprises: Organic electroluminescent device, optical sensor, solar cell, lighting element, organic thin film transistor, organic field effect transistor, organic thin film solar cell, information tag, electronic artificial skin sheet, sheet-type scanner or electronic paper.

7. Use of the compound according to any one of claims 1 to 4 as an electron transport / injection material.

8. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer contains the compound according to any one of claims 1 to 4.

9. The organic electroluminescent device according to claim 8, wherein the plurality of light-emitting functional layers include at least one of an electron injection layer, an electron transport layer or a hole blocking layer, and the electron injection layer, the electron transport layer or the hole blocking layer contains the organic compound according to any one of claims 1 to 4.

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