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 I. When the compound of the present invention is used in an organic electroluminescent device, especially as an electron blocking layer material, the device current efficiency can be effectively improved to achieve the best effect. In the compound structure of the present invention, the mother nucleus triarylamine group can effectively regulate the three-dimensional structure of the molecule and improve the packing density of the molecule; at the same time, the introduction of a substituent at the ortho position of the benzene ring can not only adjust the ortho steric hindrance, but also effectively regulate the distortion of the molecule to reduce the crystallinity of the molecule. Most importantly, when one of the aromatic groups in the triarylamine structure is a five-membered heterocyclic ring on the benzene ring, the triplet energy level of the material can be effectively improved to improve the device efficiency. .

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and 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 occupied a place in the field of information display. This is mainly due to the fact that OLED devices can use the three primary colors of red, green and blue with high saturation 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.

[0003] The core of OLED devices is a thin film structure containing a variety of organic functional materials. Common functional 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 guest (dyes).

[0004] People have developed a variety of organic materials, which, combined with various specific device structures, can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device attenuation. According to the luminescence mechanism, it can be divided into fluorescent materials that emit light through the singlet excited state of electrons and phosphorescent materials that emit light through the triplet excited state of electrons. In order to effectively alleviate the aggregation of luminescent materials and triplet excitons and avoid concentration quenching, a host-guest doping system in which luminescent materials are doped in the host material is usually adopted. The excitons generated by the host are transmitted to the dopant, thereby emitting light with high efficiency. Among them, the electron blocking material plays the role of preventing the excitons generated in the light-emitting layer from diffusing to the hole transport layer, resulting in color cast and reduced luminescence efficiency, preventing efficiency roll-off and improving the stability of the device. Therefore, in the development of luminescent materials that seek to improve the luminescence efficiency of the device, reduce the driving voltage, and extend the service life, the development of electron blocking materials has received much attention.

[0005] The application of triarylamine structure compounds in organic functional materials has always attracted much attention. For example, in patent documents WO201919292954A1 and CN110416422A, the application of the following compounds in organic functional materials is disclosed:

[0006]

[0007] However, the inventors of the present invention have found that the technical effect of the above compounds when used as electron blocking layers is still not ideal and there is still room for improvement. Therefore, people hope to develop a new compound that can be applied to OLED devices and improve device performance, and there is still a need to further develop more suitable organic functional materials. Summary of the invention

[0008] 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 inventor has devoted himself to research and developed the following organic compound to complete the present invention

[0009] Specifically, the present invention provides an organic compound, characterized in that it has a structure shown in Formula I;

[0010]

[0011] X is O, S, or CR 4 R 5 , where R 4 or R 5 Each is independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3~C 30 One of the heteroaryl groups;

[0012] Y is O or S;

[0013] L 1 Selected from single bonds, substituted or unsubstituted C6~C 12 Arylene or substituted or unsubstituted C3~C 11 heteroarylene;

[0014] Ar 1 Selected from substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C3~C 30 of heteroaryl,

[0015] R 1～ R 3 Selected from H, halogen, 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 Aryl alkoxy, C2~C 30 Alkenyl, C2~C 30Alkynyl, C1~C 30 A combination of one or more silane groups; m is an integer of 0 to 5, n is an integer of 0 to 7, and q is an integer of 1 to 3; R 1 ~R 3 A ring structure can be formed between the benzene ring to which it is connected, R 1 ~ R 3 When multiple, multiple R 2 Can be connected to form a ring, multiple R 3 They can be connected to form a ring;

[0016] The substitution in the above substituted or unsubstituted groups is selected from halogen, C1-C 17 Amino, C1~ C 12 Chain alkyl, C2~C 10 Alkenyl, C1~C 10 Alkoxy, C6~C 30 Arylamino, C3~C 30 Heteroarylamino, C6~C 30 Aryl, C3~C 30 The compound is substituted by one or more heteroaryl groups.

[0017] The inventors have found that when the above-mentioned compound of the present invention is applied to the electron blocking 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 still unclear.

[0018] The mother core structure of the compound of the present invention adopts a triarylamine structure. Since the three aromatic groups connected to the N atom are all relatively large groups, the overall structure is a helical structure, which can effectively improve the molecular packing density. When used as an organic electroluminescent material device, a stable amorphous film can be formed. At the same time, the dibenzopentacyclic structure containing X in the structure is located at the ortho position of the N-substituted group of the benzene ring, has a relatively large steric hindrance, and can effectively regulate the twisting degree of the molecule to reduce the molecular crystallinity. It is speculated that the effective regulation of the three-dimensional structure of the molecule further improves the molecular packing density, so that the electron blocking effect is more excellent.

[0019] A more important feature of the present invention is that a dibenzoheterocycle with a good planar configuration is introduced into an aromatic group connected to N, that is, a dibenzo pentacyclic structure containing Y in formula I. In other words, when a group with good planarity such as dibenzofuran or dibenzothiophene is introduced into an aromatic group connected to N, the inventors of the present invention unexpectedly found that an unexpected substantial improvement in the effects of reducing the driving voltage and improving the luminous efficiency was achieved. The reason for such an improvement is also unclear. It is speculated that such a group is directly connected to the N atomic structure of the triarylamine structure, and the good planar structure and the overall three-dimensional conformation of the compound are more conducive to the transmission of charges, thereby reducing the voltage and improving the efficiency.

[0020] It should be noted that in this specification, 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.

[0021] 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.

[0022] 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, composed of at least two heteroaromatic rings fused together, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc. In the present invention, the alkyl group may be a linear alkyl group or a branched alkyl group, and also includes the concept of a cycloalkyl group.

[0023] “R 1 ~R 3When multiple, multiple R 1 Can be connected to form a ring, multiple R 2 Can be connected to form a ring, multiple R 3 "Can be connected to form a ring" means: 1 For example, two R 1 Between or more R 1 They are connected to each other to form an aliphatic or aromatic ring structure together with the benzene ring to which they are bonded. If an aromatic ring structure is formed, they can also form a condensed ring structure together with the benzene ring to which they are connected, such as a naphthyl, anthracene, triphenylene or other structure.

[0024] In this specification, substituted or unsubstituted C6 to C 30 The aryl group is preferably C6-C 20 The 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, tetraphenylene, 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, 2- The naphthacene group is selected from the group consisting of 1-naphthacene, 2-naphthacene and 9-naphthacene.

[0025] 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.

[0026] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0027] 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: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, Phenazinyl, 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- The preferred examples of heteroaryl in the present invention include furanyl, 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.

[0028] 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.

[0029] The aryloxy group in the present invention includes a monovalent group composed of the above-mentioned aryl group and heteroaryl group and oxygen.

[0030] 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. 30 The alkyl group is typically a C1-C6 alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, and cyclohexyl.

[0031] In the present specification, the cycloalkyl group in the alkyl group includes not only a monocyclic alkyl group but also a polycyclic alkyl group, for example, decahydronaphthalene, norbornyl, and the like.

[0032] In this specification, C1 to C 30 The alkoxy group may be the above-mentioned C1~C 30 Examples of the group in which the alkyl group is connected to the oxy group 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. 30 The alkoxy group is typically an alkoxy group of the above-mentioned C1-C6 alkyl group, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy.

[0033] In this specification, C2 to C 30 The alkenyl group is typically a C2-C6 alkenyl group, and examples thereof include vinyl, propenyl, 1-butenyl, etc.; 30 The alkynyl group is typically a C2-C6 alkynyl group, and examples thereof include ethynyl, propynyl, 1-butynyl, and the like.

[0034] 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.

[0035] In the present specification, examples of halogen include fluorine, chlorine, bromine, and iodine.

[0036] More specifically, as the above-mentioned R 1 ~R 3 The group of alkyl, preferably 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, phenanthryl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, naphthacene, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenylene, terphenylene, quaterphenylene, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenylcarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, Benzo-6,7-quinolyl, benzo-7,8-quinolyl, 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-diazaanthenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, The invention can be selected from the group consisting of 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 and benzothiadiazolyl, or a combination of two of the above groups.

[0037] 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.

[0038] C1~C above 17 Amino, C1~C 17 Carboxyl, C1~C 17 Aldehyde, C1~C 17 The ester group refers to a substituted amino group, carboxyl group, aldehyde group, or ester group formed by the alkyl group, aryl group, or heteroaryl group listed above.

[0039] It is further preferred that in the structure shown in Formula I, q=1, R 1 is phenyl or naphthyl, more preferably phenyl, and further preferably R 1 The inventors found that when R 1 When it is a para-phenyl group, a lower voltage can be achieved under the same conditions.

[0040] In the compound described in the above formula I, the Ar 1 Preferably, substituted or unsubstituted C6 to C 20 Aryl or substituted or unsubstituted C3~C 20 Heteroaryl; L 1 Preferably, Ar 1 Any one selected from the following substituted or unsubstituted groups:

[0041]

[0042] When Ar 1 and L 1 When the compound of the present invention is used as an electron blocking layer, better device efficiency can be achieved. It is speculated that this effect may be due to the fact that 1 or L 1 When the position of Ar is a phenylene, biphenylene, naphthylene, or terphenylene group, it is more conducive to the transport of carriers, and while serving as an electron blocking layer, it enables effective injection of carriers such as holes, thereby achieving better device efficiency. From this point of view, it is further preferred that the Ar 1 Any one selected from the following substituted or unsubstituted groups,

[0043]

[0044] In the present invention, the above-mentioned dotted line represents the connecting bond of the group.

[0045] In the compounds of the present invention, R 2 The group of R is freely determined by those skilled in the art. From the perspective of easier availability of compounds, R 2 is a hydrogen atom, and from the same viewpoint, it is preferred that R 2 The benzene ring is located in the para position to the N substituent.

[0046] Furthermore, the organic compound of the present invention can preferably include the specific structural compounds shown in the following C1 to C147, and these compounds are only representative.

[0047]

[0048]

[0049]

[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, and it is suitable for mass production and expansion, and is very suitable for industrial application.

[0056] The above-mentioned compounds of the present invention have excellent electron blocking effects and excellent exciton blocking effects, and are particularly suitable for use as electron blocking materials. However, the application scenarios of the compounds of the present invention are not limited to electron blocking materials. They can also be used as hole transport, hole injection 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 a hole injection layer, a hole transport layer, and an electron blocking layer, wherein at least one layer selected from the hole injection layer, the hole transport layer, and the electron blocking layer contains the above-mentioned organic compound of the present invention; preferably, the electron blocking layer contains the organic compound of the present invention. DETAILED DESCRIPTION

[0059] 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.

[0060] Method for obtaining the compound of the present invention

[0061] The compound represented by the general formula I 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.

[0062]

[0063] Among them, X, Y, R 1 ~R 3 , L 1 ,Ar 1 , m, n, q have the same definitions as those in Formula I; Pd2(dba)3 represents tris(dibenzylacetone)dipalladium(0), IPr.HCl represents 1, bis(2, diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium tert-butoxide, and (t-Bu)3P represents tri-tert-butylphosphine. 1 ~R 3 , L 1 ,Ar 1 The compounds of the present invention can be synthesized by using different raw materials or customized intermediates such as m, n, and q through the above-mentioned common pathway.

[0064] The organic electroluminescent device is described in detail below.

[0065] The OLED device 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 multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[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) and aromatic amine derivatives as shown in HT-1 to HT-51 below; or any combination thereof.

[0071]

[0072]

[0073]

[0074] 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 HI-1 to HI-3 below; or one or more compounds of HT-1 to HT-51 can be doped with one or more compounds of HI-1 to HI-3 below.

[0075]

[0076] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer can 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 can be arranged in a plane according to a pixel pattern, or they can be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0077] 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.

[0078] 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.

[0079]

[0080] 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.

[0081]

[0082]

[0083] 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.

[0084]

[0085]

[0086]

[0087]

[0088] 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.

[0089]

[0090]

[0091] Where D is deuterium.

[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] The organic electroluminescent device of the present invention comprises 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).

[0099] The electron transport region can also be formed by using the compound of the present invention for 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). 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.

[0100]

[0101]

[0102]

[0103] 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.

[0104] 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:

[0105] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg.

[0106] Example

[0107] 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.

[0108] The following synthesis examples of the present invention illustratively provide specific synthesis methods for representative compounds. The solvents and reagents used in the following synthesis examples, such as 3-bromo-9,9-dimethylfluorene, 1, bis(2, diisopropylphenyl)imidazolium chloride, tri(dibenzylacetone)dipalladium(0), toluene, methanol, ethanol, tri-tert-butylphosphine, sodium tert-butyl alcohol and other chemical reagents, can all be purchased or customized from the domestic chemical product market, such as Sinopharm Reagent Company, Sigma-Aldrich Company, and J&K Reagent Company. Intermediates such as M1 to M7 can be customized by reagent companies such as J&K.

[0109] Synthesis Example 1: Synthesis of Compound C1

[0110]

[0111] In a 1L single-mouth bottle, add 9g P1, 4.68g phenylboric acid, 6.63g potassium carbonate, add toluene (100mL), ethanol (40mL), and water (30mL) and stir evenly. Replace the air in the bottle with nitrogen, then add 0.37g Pd(PPh3)4, and heat to 80 degrees under nitrogen protection for 16 hours. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. The organic phases are combined and concentrated to obtain a brown-red oil. The crude product is purified by chromatography column (petroleum ether / dichloromethane, 10 / 1) to obtain a white solid M1. The product is used directly in the next step.

[0112] In a 1L single-mouth bottle, add 20g P2, 20.51g 4-bromodibenzofuran, 16.71g potassium carbonate, add toluene (200mL), ethanol (100mL), and water (100mL) and stir evenly. Replace the air in the bottle with nitrogen, then add 0.93g Pd(PPh3)4, and heat to 80 degrees under nitrogen protection for 16 hours. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. The organic phases are combined and concentrated to obtain a brown-red oil. Stir in petroleum ether for 2 hours to precipitate a solid. The solid is stirred in 300mL petroleum ether / toluene (15 / 1) to obtain a white solid M2.

[0113] In a 250mL single-mouth bottle, add 6.0g of compound M1, 4.82g of compound M2, and 1.95g of sodium tert-butoxide, 100mL of toluene, under nitrogen protection, add catalyst 0.155g of Pd2dba3 and 0.72g of IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 10 / 1) to obtain a yellow solid. Stir in ethyl acetate and petroleum ether (1 / 20) and ethanol at 40°C, and filter to obtain a light yellow solid M3.

[0114] In a 250mL single-mouth bottle, add 7.0g of compound M3, 3.7g of 4-phenylbromobenzene and 1.8g of sodium tert-butoxide, 100mL of toluene, under nitrogen protection, add 0.11g of catalyst Pd2dba3 and 0.5mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution is passed through a short silica gel column, and rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 6 / 1) to obtain a white solid C1.

[0115] Theoretical M / Z value: 729.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 730.3 (mass spectrometry detection source is ESI source, the same below).

[0116] Synthesis Example 2: Synthesis of Compound C5

[0117]

[0118] In a 1L single-mouth bottle, add 15.0g of compound M3, 10.41g of 4-bromoterphenyl and 7.49g of sodium tert-butoxide, 600mL of toluene, and under nitrogen protection, add 1.19g of catalyst Pd2dba3 and 2mL (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials by spot plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C5.

[0119] Theoretical M / Z value: 805.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 806.3.

[0120] Synthesis Example 3: Synthesis of Compound C12

[0121]

[0122] In a 1L single-mouth bottle, add 15.0g of compound M3, 9.53g of 4-(1-naphthyl)bromobenzene and 7.49g of sodium tert-butoxide, 600mL of toluene, under nitrogen protection, add 1.19g of catalyst Pd2dba3 and 2mL of (t-Bu)3P, then heat to reflux and react overnight; spot plate monitors the complete reaction of the raw materials and cools to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 9 / 1) to obtain white solid C12.

[0123] Theoretical M / Z value: 779.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 780.3.

[0124] Synthesis Example 4: Synthesis of Compound C21

[0125]

[0126] In a 1L single-mouth bottle, add 9g P3, 4.68g phenylboric acid, 6.63g potassium carbonate, 100mL toluene, 50mL ethanol and 50mL water, and stir evenly. Replace the air in the bottle with nitrogen, then add 0.37g Pd(PPh3)4, and heat to 80°C for 16 hours under nitrogen protection. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. The organic phases are combined and concentrated to obtain a brown-red oil. The crude product is purified by chromatography column (petroleum ether / dichloromethane, 10 / 1) to obtain a white solid M4. The product is used directly in the next step.

[0127] In a 250mL single-mouth bottle, add 6.0g of compound M2, 4.82g of compound M4, 1.95g of sodium tert-butoxide and 100mL of toluene; under nitrogen protection, add catalyst 0.155g of Pd2dba3 and 0.72g of I PrHCl, then heat to reflux and react overnight. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 10 / 1) to obtain a light yellow solid. Stir in ethyl acetate and petroleum ether (1 / 20) and ethanol in turn, and filter to obtain a white solid M5.

[0128] In a 250mL single-mouth bottle, add 7.0g of compound M5, 3.7g of 4-phenylbromobenzene, 1.8g of sodium tert-butoxide and 100mL of toluene. Under nitrogen protection, add 0.11g of Pd2dba3 and 0.5mL of (t-Bu)3P. Then heat to reflux and react overnight. Monitor the reaction of the raw materials with a plate. Cool to room temperature. Pass the reaction liquid through a short silica gel column and rinse with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (using PE / DCM as the eluent = 10 / 1) to obtain a white solid C21.

[0129] Theoretical M / Z value: 729.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 730.3.

[0130] Synthesis Example 5: Synthesis of Compound C22

[0131]

[0132] In a 1L single-mouth bottle, add 15.0g of compound M5, 9.19g of 2-bromo-9,9-dimethylfluorene and 7.49g of sodium tert-butoxide, 600mL of toluene, and under nitrogen protection, add 1.19g of catalyst Pd2dba3 and 2 mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C22.

[0133] Theoretical M / Z value: 769.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 770.3.

[0134] Synthesis Example 6: Synthesis of Compound C33

[0135]

[0136] In a 1L single-mouth bottle, add 15.0g of compound M5, 9.73g of 4-tert-butyl 2-phenyl bromobenzene and 7.49g of sodium tert-butoxide, 600mL of toluene, under nitrogen protection, add 1.19g of catalyst Pd2dba3 and 2 mL of (t-Bu)3P, then heat to reflux and react overnight; spot plate monitors the complete reaction of the raw materials and cools to room temperature. The reaction liquid passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 7 / 1) to obtain a white solid C33.

[0137] Theoretical M / Z value: 785.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 786.3.

[0138] Synthesis Example 7: Synthesis of Compound C61

[0139]

[0140] In a 1L single-mouth bottle, add 20g P4, 8.24g phenylboric acid, 18.65g potassium carbonate, 400mL toluene, 200mL ethanol and 200mL water, and stir evenly. Replace the air in the bottle with nitrogen, then add 1.56g Pd(PPh3)4, and heat to 80°C under nitrogen protection to react overnight. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. The organic phases are combined and concentrated to obtain a brown-red oil. The crude product is purified by chromatography column (petroleum ether / dichloromethane, 10 / 1) to obtain a white solid M6. The product is dried and used directly in the next step.

[0141] In a 250mL single-mouth bottle, add 8.0g of compound M2, 7.02g of compound M6, 6.87g of sodium tert-butoxide and 500mL of toluene; under nitrogen protection, add catalyst 0.22g of Pd2dba3 and 0.21g of IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 9 / 1) to obtain a light yellow solid. Stir in ethyl acetate and petroleum ether (1 / 20) and ethanol in turn, and filter to obtain a light yellow solid M7.

[0142] In a 250mL single-mouth bottle, add 5.0g of compound M7, 2.54g of 4-phenylbromobenzene, 2.43g of sodium tert-butoxide and 100mL of toluene. Under nitrogen protection, add 0.38g of Pd2dba3 and 1mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials by spot plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 9 / 1) to obtain a white solid C61.

[0143] Theoretical M / Z value: 745.2; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 746.3.

[0144] Synthesis Example 8: Synthesis of Compound C81

[0145]

[0146] In a 1L single-mouth bottle, add 20g P2, 22.02g 2-bromo-9,9-dimethylfluorene, 22.35g potassium carbonate, add toluene (400mL), ethanol (200mL), and water (200mL) and stir evenly. Replace the air in the bottle with nitrogen, then add 1.87g Pd(PPh3)4, and heat to 80 degrees under nitrogen protection to react overnight. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. Combine the organic phases and spin off the solvent. Stir in petroleum ether for 2 hours to precipitate a solid. The solid is stirred in 300mL petroleum ether / toluene (15 / 1) to obtain a white solid M8.

[0147] In a 250mL single-mouth bottle, add 7.22g of compound M8, 5.56g of compound M1, and 8.64g of sodium tert-butoxide, 300mL of toluene, under nitrogen protection, add catalyst 0.18g Pd2dba3 and 0.17g IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 6 / 1) to obtain an off-white solid. Stir in petroleum ether and ethanol at 40°C, and filter to obtain a white solid M9.

[0148] In a 250mL single-mouth bottle, add 6.0g of compound M9, 3.92g of 4-phenylbromobenzene and 2.86g of sodium tert-butoxide, 100mL of toluene, and under nitrogen protection, add 0.46g of catalyst Pd2dba3 and 1mL (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C81.

[0149] Theoretical M / Z value: 755.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 756.3.

[0150] Synthesis Example 9: Synthesis of Compound C88

[0151]

[0152] In a 1L single-mouth bottle, add 15g of compound M9, 9.12g of 4-(1-naphthyl)bromobenzene and 7.16g of sodium tert-butoxide, 500mL of toluene, and under nitrogen protection, add 1.14g of catalyst Pd2dba3 and 2mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C88.

[0153] Theoretical M / Z value: 805.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 806.3.

[0154] Synthesis Example 10: Synthesis of Compound C100

[0155]

[0156] In a 1L single-mouth bottle, add 15g of compound M9, 9.12g of 4-(2-naphthyl)bromobenzene and 7.16g of sodium tert-butoxide, 500mL of toluene, and under nitrogen protection, add 1.14g of catalyst Pd2dba3 and 2mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials by spot plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C100.

[0157] Theoretical M / Z value: 805.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 806.3.

[0158] Synthesis Example 11: Synthesis of Compound C102

[0159]

[0160] In a 250mL single-mouth bottle, add 7.22g of compound M8, 5.56g of compound M4, and 8.64g of sodium tert-butoxide, 300mL of toluene, under nitrogen protection, add catalyst 0.18g Pd2dba3 and 0.17g IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 6 / 1) to obtain an off-white solid. Stir in petroleum ether and ethanol at 40°C, and filter to obtain a white solid M10.

[0161] In a 250mL single-mouth bottle, add 6.0g of compound M10, 3.52g of 2-bromo-9,9-dimethylfluorene and 2.86g of sodium tert-butoxide, 100mL of toluene, under nitrogen protection, add 0.46g of catalyst Pd2dba3 and 1mL (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 10 / 1) to obtain a white solid C102.

[0162] Theoretical M / Z value: 795.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 796.3.

[0163] Synthesis Example 12: Synthesis of Compound C118

[0164]

[0165] In a 1L single-mouth bottle, add 20g P2, 22.02g 3-bromo-9,9-dimethylfluorene, 22.35g potassium carbonate, add toluene (400mL), ethanol (200mL), and water (200mL) and stir evenly. Replace the air in the bottle with nitrogen, then add 1.87g Pd(PPh3)4, and heat to 80 degrees under nitrogen protection to react overnight. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. Combine the organic phases and spin off the solvent. Stir in petroleum ether for 2 hours to precipitate a solid. The solid is stirred in 300mL petroleum ether / toluene (10 / 1) to obtain a white solid M11.

[0166] In a 250mL single-mouth bottle, add 7.22g of compound M11, 5.56g of compound M4, and 8.64g of sodium tert-butoxide, 300mL of toluene, under nitrogen protection, add catalyst 0.36g of Pd2dba3 and 0.34g of IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 10 / 1) to obtain a white solid. Stir in petroleum ether and ethanol at 40°C, and filter to obtain a white solid M12.

[0167] In a 250mL single-mouth bottle, add 6.0g of compound M12, 3.98g of 3,4-diphenylbromobenzene and 2.86g of sodium tert-butoxide, 100mL of toluene, under nitrogen protection, add 0.46g of catalyst Pd2dba3 and 1mL (t-Bu)3P, then heat to reflux and react overnight; spot plate monitors the complete reaction of the raw materials and cools to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 9 / 1) to obtain a white solid C118.

[0168] Theoretical M / Z value: 831.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 832.3.

[0169] Synthesis of comparative compounds

[0170] The following comparative compounds were synthesized at the same time:

[0171]

[0172] The specific synthesis method is as follows:

[0173] Synthesis of compound R1:

[0174] In a 250mL single-mouth bottle, add 13.0g of compound M2, 7.26g of bromobenzene, 7.45g of sodium tert-butoxide and 500mL of toluene; under nitrogen protection, add catalyst 0.70g of Pd2dba3 and 0.70g of IPrHCl, and then heat to reflux for overnight reaction. The plate was used to monitor the complete reaction of the raw materials and the temperature was lowered to room temperature. The crude product was directly purified on a silica gel column (PE / DCM, 9 / 1) to obtain a white solid. Stir in n-hexane and methanol in turn, and filter to obtain a white solid M13.

[0175] In a 250mL single-mouth bottle, add 5.0g of compound M13, 3.85g of 2,4-diphenylchlorobenzene, 2.33g of sodium tert-butoxide and 100mL of toluene. Under nitrogen protection, add 0.22g of Pd2dba3 and 0.5mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials with a plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 9 / 1) to obtain a white solid R1.

[0176] Theoretical M / Z value: 639.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 640.2.

[0177] Synthesis of compound R2:

[0178]

[0179] In a 250mL single-mouth bottle, add 5.0g of compound M13, 3.97g of 4-bromo-9,9-dimethylfluorene, 2.33g of sodium tert-butoxide and 100mL of toluene. Under nitrogen protection, add 0.22g of Pd2dba3 and 0.5 mL of (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials by spot plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 9 / 1) to obtain a white solid R2.

[0180] Theoretical M / Z value: 603.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 604.3.

[0181] Synthesis of compound R3:

[0182]

[0183] In a 2L single-mouth bottle, add 30g P5, 39.64g 2-bromo-9,9-dimethylfluorene, 33.76g potassium carbonate, add toluene (400mL), ethanol (200mL), and water (200mL) and stir evenly. Replace the air in the bottle with nitrogen, then add 2.75g Pd(PPh3)4, and heat to 100℃ under nitrogen protection to react overnight. After monitoring the reaction is complete, cool down, pour the reaction solution into water, and extract with ethyl acetate until there is no product in the aqueous phase. Combine the organic phases and spin to remove the solvent. Stir in petroleum ether for 2 hours to precipitate a solid. The solid is stirred in 600mL petroleum ether / toluene (10 / 1) to obtain a white solid M14.

[0184] In a 1L single-mouth bottle, add 15g compound M14, 16.84g 4-(dibenzothiophene-1-yl) bromobenzene, and 11.97g sodium tert-butoxide, 600mL toluene, under nitrogen protection, add catalyst 1.9g Pd2dba3 and 1.8g IPrHCl, and then heat to reflux reaction overnight. The plate is used to monitor the complete reaction of the raw materials and the temperature is lowered to room temperature. The crude product is directly purified on a silica gel column (PE / DCM, 10 / 1) to obtain a white solid. Stir in petroleum ether and ethanol at 40°C, and filter to obtain a white solid M15.

[0185] In a 500mL single-mouth bottle, add 12.4g of compound M15, 6.53g of 4-bromo-9,9-dimethylfluorene and 5.76g of sodium tert-butoxide, 200mL of toluene, under nitrogen protection, add 0.92g of catalyst Pd2dba3 and 2mL (t-Bu)3P, then heat to reflux and react overnight; monitor the reaction of the raw materials by spot plate, and cool to room temperature. The reaction solution passes through a short silica gel column and is rinsed with toluene as the eluent until there is no product. After concentration, a brown-red oil is obtained. Purify by column chromatography (eluent PE / DCM = 6 / 1) to obtain a white solid R3.

[0186] Theoretical M / Z value: 811.3; measured M / Z value using ZAB-HS mass spectrometer (manufactured by Micromass, UK): 812.3.

[0187] Device Example 1

[0188] This embodiment 1 provides a method for preparing an organic electroluminescent device, which is as follows:

[0189] The glass plate coated with the ITO transparent conductive layer (as the anode) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum of less than 1×10-5 Pa, a mixture of HT-4:HI-3 (97 / 3, w / w) was vacuum-deposited on the above-mentioned anode layer as a hole injection layer, the deposition rate was 0.1 nm / s, and the deposition film thickness was 10 nm; HT-4 was vacuum-deposited on the hole injection layer as a hole transport layer of the device, the deposition rate was 0.1 nm / s, and the total deposition film thickness was 60 nm; compound C1 was vacuum-deposited on the hole transport layer as the electron blocking layer material of the device, the deposition rate was 0.1 nm / s, and the total deposition film thickness was 5 nm.

[0190] The light-emitting layer of the device is vacuum-deposited on the electron blocking layer. The light-emitting layer includes a main material and a dye material. The evaporation rate of the main material BFH-4 is adjusted to 0.1nm / s, and the evaporation rate of the dye BFD-3 is set to 3% of the main material by a multi-source co-evaporation method. The total evaporation film thickness is 20nm; the electron transport layer materials ET-61 and ET-57 of the device are vacuum-deposited on the light-emitting layer. The mass ratio of the two is 1:1. The evaporation rate is 0.1nm / s, and the total evaporation film thickness is 20nm; LiF with a thickness of 0.5nm is vacuum-deposited on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150nm is used as the cathode of the device.

[0191] The only difference between device examples 2-16 and device example 1 is that the compound C1 of the present invention used in the electron blocking layer is replaced by other compounds of the present invention, as shown in Table 1 for details.

[0192] The preparation process of the organic electroluminescent devices provided in device comparison examples 1-3 is the same as that in Example 1, except that the material compound C1 used in the electron blocking layer is replaced by compounds R1 to R4 in the prior art, respectively. The structural formulas of the specific compounds are shown above, and these compounds are obtained based on the methods described in the corresponding patent documents.

[0193] Performance Testing:

[0194] (1) At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in the examples and comparative examples and the life of the devices were measured using a digital source meter (Keithley 2400) and a brightness meter (ST-86LA brightness meter, Beijing Normal University Optoelectronic Instrument Factory). Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 1000 cd / m 2 The voltage at this time is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency;

[0195] (2) The life test of LT97 is as follows: Use a luminance meter at 1000cd / m 2Under the same brightness, keep a constant current and measure the time for the brightness of the organic electroluminescent device to drop to 97%, in hours.

[0196] The performance test results are shown in Table 1.

[0197] Table 1:

[0198]

[0199] It can be seen from the data in Table 1 that when the material scheme and preparation process of other functional layers in the structure of the organic electroluminescent device are exactly the same, when the compound of the present invention is used as the electron blocking layer material of the organic electroluminescent device, the brightness of the device reaches 1000 cd / m 2 When the driving voltage is as low as below 4.0V, the current efficiency is as high as above 9cd / A. The current efficiency of the device is significantly improved compared with the comparative device using the compound in the prior art as the electron blocking layer material, which helps to improve the low efficiency problem of the current OLED blue light device, thereby reducing power consumption and having better practicality. It can be seen that the compound of the present invention is indeed an electron blocking layer material with good performance.

[0200] The difference between the compound R1 used in comparative example 1 and the compound of the present invention is that the substituents are all freely rotatable single bond connections, and the molecular rigidity is lower than that of the group used in the present invention; at the same time, due to the free rotation of the substituents in the molecule, the planarity of the material is reduced and the transmission capacity is reduced; when the compound R1 is used as an electron blocking layer material for an organic electroluminescent device, the driving voltage of the device is 4.02V and the current efficiency is 7.48cd / A. This can be attributed to the reduction in the hole transmission capacity and molecular rigidity of the compound R1 itself, which leads to a decrease in photoelectric performance.

[0201] The difference between the compounds R2-R3 used in Comparative Examples 2-3 and the compounds described in the present invention is that 9,9-dimethylfluorene is introduced as a substituent in the structure of the compounds R2-R3. Due to the stereoscopic structure of the methyl group in fluorene, the planarity of the material is reduced, the film-forming density is reduced, and it is not conducive to the improvement of device performance. When the compounds R2-R3 are used as electron blocking layer materials for organic electroluminescent devices, the device current efficiency is lower than the efficiency of the device prepared by the compounds described in the present invention, and the life is shorter. This is because the difference in the film-forming properties of the compounds leads to a decrease in hole transport performance, which in turn leads to a decrease in device efficiency.

[0202] The difference between the compound R4 used in comparative example 4 and the compound described in the present invention is that 9,9-dimethylfluorene is introduced as a substituent in the structure of the compound R4. When the compound R4 is used as an electron blocking layer material for an organic electroluminescent device, the device current efficiency is lower than the efficiency of the device prepared by the compound described in the present invention, and the life span is shorter. This may be because the present invention uses an O or S-containing heterocyclic group connected to the central N atom, which has better stability and electron tolerance than the group used in R4, thereby improving the device performance.

[0203] 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.

[0204] 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 It has the structure shown in Formula I; the structure is the structure shown below, X is O, S, or CR 4 R 5 , where R 4 or R 5 Each is independently selected from H, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3~C 30 One of the heteroaryl groups; Y is O or S; L 1 is a single bond, a phenylene group, or a biphenylene group; Ar 1 Selected from substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C3~C 30 heteroaryl; R 1 Selected from substituted or unsubstituted C6~C 30 Aryl; q=1 and R 1 Located at the para position of the N substituent, m=0 or 1, n=0, t=1; R 2 is a hydrogen atom, R 3 is a hydrogen atom, The above substituted or unsubstituted groups are substituted by halogen, C1-C 17 Amino, C1~C 12 Alkyl, C2~C 10 Alkenyl, C1~C 10 Alkoxy, C6~C 30 Arylamino, C3~C 30 Heteroarylamino, C6~C 30 Aryl, C3~C 30 The compound is substituted by one or more heteroaryl groups.

2. The compound according to claim 1, wherein in the structure shown in Formula I, Ar 1 Selected from substituted or unsubstituted C6~C 20 Aryl or substituted or unsubstituted C3~C 20 Heteroaryl.

3. The compound according to claim 1, wherein in the structure shown in Formula I, Ar 1 Any one selected from the following substituted or unsubstituted groups: in, Dashed lines represent bonds connecting groups.

4. The compound according to claim 1, wherein in Formula I, R 2 The attached benzene ring is located in the para position to the N substituent.

5. A compound having the structure shown below: 6 . An organic electroluminescent material, which is the compound according to claim 1 . 7 . An electron blocking layer material, which is the compound according to claim 1 .

8. Use of the compound according to any one of claims 1 to 5 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.

9. Use of the compound according to any one of claims 1 to 5 as an electron blocking layer material.

10. 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 5.

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