WO2024051479A1

WO2024051479A1 - Organic electroluminescent device and electronic apparatus

Info

Publication number: WO2024051479A1
Application number: PCT/CN2023/113868
Authority: WO
Inventors: 徐先彬; 杨雷
Original assignee: 陕西莱特光电材料股份有限公司
Priority date: 2022-09-08
Filing date: 2023-08-18
Publication date: 2024-03-14
Also published as: CN117396015A

Abstract

An organic electroluminescent device and an electronic apparatus. The organic electroluminescent device comprises a cathode (200), an anode (100), and an organic layer. The organic layer comprises an organic light-emitting layer (330), wherein the organic light-emitting layer (330) comprises a first compound and a second compound; the first compound is selected from a compound as represented by formula (1); and the second compound is selected from a compound as represented by formula (2).

Description

Organic electroluminescent devices and electronic devices

Cross-references to related applications

This application claims priority from the Chinese patent application with application number CN202211095629.X submitted on September 8, 2022. The full text of the above Chinese patent application is hereby cited as part of this application.

Technical field

The present application relates to the technical field of organic electroluminescent materials, and in particular to an organic electroluminescent device and an electronic device.

Background technique

In recent years, organic electroluminescent devices (OLED) have become a very popular emerging flat-panel display product at home and abroad. This is because OLED displays have the characteristics of self-illumination, wide viewing angle, short response time, high efficiency, and wide color gamut.

Organic electroluminescent devices (OLEDs) generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer may include a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a light emitting layer (containing host and dopant materials), a hole blocking layer, an electron transport layer, an electron injection layer, etc. When a voltage is applied to the organic electroluminescent device, holes and electrons are injected into the light-emitting layer from the anode and cathode respectively. Then, in the light-emitting layer, the injected holes and electrons recombine to form excitons. The excitons release energy in the excited state, causing the luminescent layer to emit light.

At present, there are still problems with insufficient performance in the use of organic electroluminescent devices, such as driving voltage that is too high, luminous efficiency that is too low, or lifespan is short, etc., which all affect the use areas of electromechanical light-emitting devices. Therefore, , further research in this area is still necessary to improve the performance of organic electroluminescent devices.

Contents of the invention

In view of the above-mentioned problems existing in the prior art, the purpose of this application is to provide an organic electroluminescent device and an electronic device to improve the performance of the device and device.

According to a first aspect of the present application, an organic electroluminescent device is provided, including a cathode, an anode and an organic layer;

Wherein, the cathode and the anode are arranged oppositely;

The organic layer is located between the cathode and the anode;

The organic layer includes an organic light-emitting layer;

The organic light-emitting layer includes a first compound and a second compound;

The first compound has the structure shown in Formula 1:

Among them, Y is selected from S or O;

One of X ₁ and X ₂ is -N=, the other is O or S;

Ring A is selected from naphthalene ring or phenanthrene ring;

L, L ₁ and L ₂ are the same or different, and are each independently selected from single bonds, substituted or unsubstituted arylene groups with 6 to 30 carbon atoms, carbon Substituted or unsubstituted heteroarylene group with 3 to 30 atoms;

Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are each independently selected from a substituted or unsubstituted aryl group with 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group with 3 to 40 carbon atoms. ;

The substituents in L, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are each independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, Haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, 6 to 10 carbon atoms 20 aryl group, deuterated aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, 1 to 10 carbon atoms Alkoxy group, alkylthio group with 1 to 10 carbon atoms, aryloxy group with 6 to 20 carbon atoms or arylthio group with 6 to 20 carbon atoms; optionally, any two adjacent The substituents form a saturated or unsaturated 3 to 15-membered ring;

Each R ₁ is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, halogenated alkyl group with 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Deuterated alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms or carbon Cycloalkyl group with 3 to 10 atoms; optionally, any two adjacent R _1s form a ring; n ₁ represents the number of R _1s ; n ₁ is selected from 0, 1, 2, 3, 4, and 5 , 6, 7, 8 or 9;

The second compound has the structure shown in Formula 2:

Wherein, Z ₁ , Z ₂ and Z ₃ are each independently selected from N or C(H), and at least one of Z ₁ to Z ₃ is N;

Groups in formula 2 Selected from the structures shown in a-1 to a-4,

One of U ₁ and U ₂ is -N=, the other is O or S; T is selected from O or S;

L ₃ , L ₄ and L ₅ are the same or different, and are each independently selected from single bonds, substituted or unsubstituted arylene groups with 6 to 30 carbon atoms, substituted or unsubstituted arylene groups with 3 to 30 carbon atoms. of heteroarylene;

Ar ₄ , Ar ₅ and Ar ₆ are the same or different, and are each independently selected from a substituted or unsubstituted aryl group with 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group with 3 to 40 carbon atoms. ;

The substituents in L ₃ , L ₄ , L ₅ , Ar ₄ , Ar ₅ and Ar ₆ are the same or different, and are each independently selected from deuterium, cyano group, halogen group, and alkyl group with 1 to 10 carbon atoms. , haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, 6 carbon atoms Aryl groups with ~20, deuterated aryl groups with 6 to 20 carbon atoms, heteroaryl groups with 3 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, 1 to 10 carbon atoms an alkoxy group, an alkylthio group with 1 to 10 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, or an arylthio group with 6 to 20 carbon atoms; optionally, any two adjacent The substituents form a saturated or unsaturated 3 to 15-membered ring;

Each R ₂ is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms. 10 deuterated alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, or Cycloalkyl group with 3 to 10 carbon atoms; n ₂ represents the number of R ₂ , n ₂ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

According to a second aspect of the present application, an electronic device is provided, including the organic electroluminescent device described in the first aspect.

According to a third aspect of the present application, a light-emitting layer composition is provided, which includes a first compound and a second compound, and the mass ratio of the first compound to the second compound is 30:70˜70:30.

The main material of the emitting layer of the organic electroluminescent device of the present application includes the first compound and the second compound. The first compound has benzodibenzofuran (or thiophene) and oxazole (or thiazole) condensed. The structure in which the parent core is connected to an aromatic amine has strong hole transport properties, and the second compound has a structure in which a fused benzoxazole (or thiazole) is connected to a triazine and has strong electron transport properties. The two are mixed to form the host material. First of all, both the hole-transporting host material and the electron-transporting host material used in this application have a relatively large conjugated system, which on the one hand can reduce the first excited triplet energy level of the compound, and on the other hand helps to enhance the hole The molecular interaction between the transport-type host material and the electron-transport type host material can form an exciplex more effectively, improve the carrier mobility, thereby improving the energy transfer efficiency of the host material to the doped material, and ultimately improving the device performance. Luminous efficiency. Secondly, in the first compound used in this application, the mother core in the mother core is connected to an aromatic amine, which can limit the LUMO (lowest unoccupied orbital) electron cloud distribution of the compound to benzodibenzofuran (or thiophene) and oxazole ( or thiazole) part, which inhibits the attack of excitons on the carbon-nitrogen bonds in the aromatic amine, thereby improving the lifetime of the device.

Description of the drawings

The accompanying drawings are used to provide a further understanding of the present application and constitute a part of the specification. They are used to explain the present application together with the following specific embodiments, but do not constitute a limitation of the present application.

Figure 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present application.

FIG. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Reference signs
100, anode 200, cathode 300, functional layer 310, hole injection layer
321. Hole transport layer 322. Hole adjustment layer 330. Organic light emitting layer 340. Electron transport layer
350. Electron injection layer 400. Electronic device

Detailed ways

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in various forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concepts of the example embodiments. be communicated to those skilled in the art. The described features, structures or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to provide a thorough understanding of embodiments of the present application.

In the figures, regions and layer thicknesses may be exaggerated for clarity. The same reference numerals in the drawings represent the same or similar structures, and thus their detailed descriptions will be omitted.

In a first aspect, this application provides an organic electroluminescent device, including a cathode, an anode and an organic layer;

Wherein, the cathode and the anode are arranged oppositely;

The organic layer is located between the cathode and the anode;

The organic layer includes an organic light-emitting layer;

The first compound has the structure shown in Formula 1:

Among them, Y is selected from S or O;

One of X ₁ and X ₂ is -N=, the other is O or S;

Ring A is selected from naphthalene ring or phenanthrene ring;

L, L ₁ and L ₂ are the same or different, and are each independently selected from a single bond, a substituted or unsubstituted arylene group with 6 to 30 carbon atoms, a substituted or unsubstituted group with 3 to 30 carbon atoms. heteroarylene;

The second compound has the structure shown in Formula 2:

Groups in formula 2 Selected from the structures shown in a-1 to a-4,

One of U ₁ and U ₂ is -N=, the other is O or S; T is selected from O or S;

The substituents in L ₃ , L ₄ , L ₅ , Ar ₄ , Ar ₅ and Ar ₆ are the same or different, and are each independently selected from deuterium, cyano group, halogen group, and alkyl group with 1 to 10 carbon atoms. , haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, 6 carbon atoms Aryl groups with ~20, deuterated aryl groups with 6 to 20 carbon atoms, heteroaryl groups with 3 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, 1 to 10 carbon atoms Alkoxy group, alkylthio group with 1 to 10 carbon atoms, carbon original An aryloxy group with 6 to 20 substituents or an arylthio group with 6 to 20 carbon atoms; optionally, any two adjacent substituents form a saturated or unsaturated 3 to 15-membered ring;

Each R ₂ is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms. 10 deuterated alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, or Cycloalkyl group with 3 to 10 carbon atoms; n ₂ represents the number of R ₂ , and n ₂ is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

In this application, the terms "optionally" and "optionally" mean that the subsequently described events or circumstances may or may not occur. For example, "optionally, any two adjacent substituents form a saturated or unsaturated 3-15-membered ring" includes: the situation where any two adjacent substituents form a ring, and any two adjacent substituents form a ring. The substituents exist independently and do not form a ring. "Any two adjacent atoms" can include two substituents on the same atom, and can also include one substituent on two adjacent atoms; where, when there are two substituents on the same atom, both Each substituent can form a saturated or unsaturated spiro ring with the atom it is connected to together; when two adjacent atoms each have a substituent, the two substituents can be fused to form a ring.

In this application, the description methods "each...independently is" and "...respectively and independently are" and "...each independently is" are interchangeable, and should be understood in a broad sense. They can both refer to In different groups, the specific options expressed by the same symbols do not affect each other. It can also mean that in the same group, the specific options expressed by the same symbols do not affect each other. For example, Among them, each q is independently 0, 1, 2 or 3, and each R" is independently selected from hydrogen, deuterium, fluorine, and chlorine. The meaning is: Formula Q-1 represents that there are q substituents R" on the benzene ring. , each R” can be the same or different, and the options of each R” do not affect each other; Formula Q-2 indicates that there are q substituents R” on each benzene ring of biphenyl, and the R on the two benzene rings "The number of substituents q can be the same or different, each R" can be the same or different, and the options for each R" do not affect each other.

In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have a substituent (hereinafter, for convenience of description, the substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The above-mentioned substituent Rc may be, for example, deuterium, cyano group, halogen group, alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, or deuterium having 1 to 10 carbon atoms. Alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, deuterated aryl group with 6 to 20 carbon atoms, carbon atom Heteroaryl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, and An aryloxy group with 6 to 20 carbon atoms or an arylthio group with 6 to 20 carbon atoms, etc. The number of substitutions can be one or more.

In this application, "plurality" refers to more than 2, such as 2, 3, 4, 5, 6, etc.

In this application, the number of carbon atoms of a substituted or unsubstituted functional group refers to the number of all carbon atoms.

The hydrogen atoms in the compound structure of the present application include various isotope atoms of the hydrogen element, such as hydrogen (H), deuterium (D) or tritium (T).

In this application, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group can be a single-ring aryl group (such as phenyl) or a polycyclic aryl group. In other words, the aryl group can be a single-ring aryl group, a fused-ring aryl group, or two or more single-ring aryl groups conjugated through a carbon-carbon bond. Ring aryl groups, monocyclic aryl groups conjugated through carbon-carbon bonds and fused-ring aryl groups, two or more fused-ring aryl groups conjugated through carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in this application. Among them, the condensed ring aryl group may include, for example, bicyclic condensed aryl group (such as naphthyl), tricyclic condensed aryl group (such as phenanthrenyl, fluorenyl, anthracenyl), etc. Aryl groups do not contain heteroatoms such as B, N, O, S, P, Se and Si. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, fluorenyl, spirobifluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, triphenylene, perylene, benzo[9,10 ]phenanthrenyl, pyrenyl, benzofluoranthene, Key et al.

In this application, the arylene group refers to a bivalent or multivalent group formed by further losing one or more hydrogen atoms from an aryl group.

In this application, terphenyl includes

In this application, the number of carbon atoms of the substituted or unsubstituted aryl group (arylene group) can be 6, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40. In some embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; in other embodiments, the substituted or unsubstituted aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. 25 substituted or unsubstituted aryl groups; in other embodiments, the substituted or unsubstituted aryl groups are substituted or unsubstituted aryl groups with carbon atoms of 6 to 18; in other embodiments, the substituted or unsubstituted aryl groups The aryl group is a substituted or unsubstituted aryl group with 6 to 15 carbon atoms.

In this application, the fluorenyl group can be substituted by one or more substituents. In the case where the above fluorenyl group is substituted, the substituted fluorenyl group can be: etc., but are not limited to this.

In this application, aryl groups as substituents include, but are not limited to, phenyl, naphthyl, phenanthrenyl, biphenyl, fluorenyl, dimethylfluorenyl, and the like.

In this application, heteroaryl refers to a monovalent aromatic ring or its derivatives containing 1, 2, 3, 4, 5 or 6 heteroatoms in the ring. The heteroatoms can be B, O, N, P, Si, One or more of Se and S. A heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, a heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated through carbon-carbon bonds, and any aromatic The ring system is an aromatic single ring or an aromatic fused ring. By way of example, heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyridyl Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thiophenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, silicon fluorenyl, dibenzofuranyl and N-phenylcarbazolyl, N-pyridine carbazolyl, N-methylcarbazolyl, etc., but are not limited thereto.

In this application, the heteroarylene group refers to a bivalent or multivalent group formed by the heteroaryl group further losing one or more hydrogen atoms.

In this application, the number of carbon atoms of the substituted or unsubstituted heteroaryl group (heteroarylene group) can be selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40. In some embodiments, the substituted or unsubstituted heteroaryl group is a substituted or unsubstituted heteroaryl group with a total carbon number of 3 to 30; in other embodiments, the substituted or unsubstituted heteroaryl group has a total carbon number of A substituted or unsubstituted heteroaryl group having 12 to 18 atoms; in other embodiments, the substituted or unsubstituted heteroaryl group is a substituted or unsubstituted heteroaryl group having a total carbon number of 5 to 12 carbon atoms.

In this application, heteroaryl groups as substituents include, but are not limited to, pyridyl, carbazolyl, dibenzothienyl, dibenzofuranyl, benzoxazolyl, benzothiazolyl, and benzimidazolyl. .

In this application, the substituted heteroaryl group may be one or more hydrogen atoms in the heteroaryl group substituted by deuterium atoms, halogen groups, cyano groups, aryl groups, heteroaryl groups, trialkylsilyl groups, alkyl groups, etc. , cycloalkyl, haloalkyl, deuterated alkyl and other groups substituted.

In this application, the alkyl group having 1 to 10 carbon atoms may include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms. The number of carbon atoms of the alkyl group may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc.

In this application, the halogen group can be, for example, fluorine, chlorine, bromine, or iodine.

In this application, specific examples of trialkylsilyl include, but are not limited to, trimethylsilyl, triethylsilyl, etc.

In this application, specific examples of haloalkyl groups include, but are not limited to, trifluoromethyl.

In this application, the number of carbon atoms of the cycloalkyl group having 3 to 10 carbon atoms may be, for example, 3, 4, 5, 6, 7, 8, 9 or 10. Specific examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, and adamantyl.

In this application, the number of carbon atoms of the deuterated alkyl group having 1 to 10 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specific examples of deuterated alkyl groups include, but are not limited to, trideuterated methyl.

In this application, the number of carbon atoms of the haloalkyl group having 1 to 10 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specific examples of haloalkyl groups include, but are not limited to, trifluoromethyl.

In this application, a ring system formed by n atoms is an n-membered ring. For example, phenyl is a 6-membered ring. A 3- to 15-membered ring refers to a cyclic group with 3 to 15 ring atoms. Examples of 3- to 15-membered rings include cyclopentane, cyclohexane, fluorene ring, and benzene ring.

In this application, Refers to the chemical bond that connects other groups to each other.

In this application, the single bond extending from the ring system involved in the connecting key is not located. It means that one end of the bond can be connected to any position in the ring system that the bond penetrates, and the other end is connected to the rest of the compound molecule. For example, as shown in the following formula (f), the naphthyl group represented by the formula (f) is connected to other positions of the molecule through two non-positioned bonds that penetrate the bicyclic ring, and its meaning includes such as the formula (f) -1) to any possible connection method shown in formula (f-10):

For another example, as shown in the following formula (X'), the dibenzofuryl group represented by the formula (X') is connected to other positions of the molecule through an unpositioned bond extending from the middle of one side of the benzene ring, Its meaning includes any possible connection method shown in formula (X'-1) to formula (X'-4):

A non-positioned substituent in this application refers to a substituent connected through a single bond extending from the center of the ring system, which means that the substituent can be connected at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by the formula (Y) is connected to the quinoline ring through a non-positioned bond, and its meaning includes such as formula (Y-1) to Any possible connection method shown in formula (Y-7):

In some embodiments, in the first compound, the group Selected from the following structures shown in a-5 to a-16:

Among them, Y is O or S.

In some embodiments, the first compound is selected from the following structures 1-2 to 1-8:

In some embodiments, in the first compound, Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and each is independently selected from the group consisting of 6, 7, 8, 9, 10, 11, 12, 13, and 14 carbon atoms. ,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39 Or 40 substituted or unsubstituted aryl groups with carbon atoms of 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 , 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40 substituted or unsubstituted heteroaryl.

In some embodiments, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and each is independently selected from deuterium, halogen group, cyano group, haloalkyl group with 1 to 4 carbon atoms, carbon atoms Deuterated alkyl group with 1 to 4 carbon atoms, alkyl group with 1 to 4 carbon atoms, cycloalkyl group with 5 to 10 carbon atoms, aryl group with 6 to 15 carbon atoms, 5 carbon atoms Heteroaryl groups with ~12, trialkylsilyl groups with 3 to 8 carbon atoms, or deuterated aryl groups with 6 to 15 carbon atoms, optionally, any two adjacent substituents form a benzene ring or Fluorene ring.

In some embodiments, in the first compound, Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and each is independently selected from substituted or unsubstituted The group W ₁ ; the unsubstituted group W ₁ is selected from the group consisting of the following groups:

The substituted group W ₁ has one or more substituents, and the substituents are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, and cyclopentyl. , cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl or carbazolyl, and when the group W ₁ When the number of substituents on is greater than 1, each substituent may be the same or different.

In some embodiments, in the first compound, Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and each is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted Substituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carb Azolyl group, substituted or unsubstituted benzothiazolyl group, substituted or unsubstituted benzoxazolyl group, substituted or unsubstituted benzimidazolyl group.

Alternatively, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, Cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothienyl or carbazolyl, Optionally, any two adjacent substituents in Ar ₁ and Ar ₂ form a benzene ring.

In some embodiments, in the first compound, Ar ₁ and Ar ₂ are the same or different, and each is independently selected from the following groups:

Ar ₃ is selected from the following groups:

In some embodiments, in the first compound, Ar ₁ and Ar ₂ are the same or different, and are each independently selected from the group consisting of the following groups:

In some embodiments, in the first compound, Ar ₃ is selected from the group consisting of:

In some embodiments, in the first compound, L, L ₁ and L ₂ are the same or different, and are each independently selected from the group consisting of single bonds and carbon atoms of 6, 7, 8, 9, 10, 11, 12, 13 , substituted or unsubstituted arylene group with 14 or 15 carbon atoms, substituted or unsubstituted arylene group with 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms of heteroarylene.

Optionally, the substituents in L, L ₁ and L ₂ are the same or different, and are each independently selected from deuterium, fluorine, cyano group, alkyl group with 1 to 5 carbon atoms, and 3 to 8 carbon atoms. trialkylsilyl group, fluoroalkyl group with 1 to 4 carbon atoms, deuterated alkyl group with 1 to 4 carbon atoms, phenyl or naphthyl group.

In some embodiments, in the first compound, L, L ₁ and L ₂ are the same or different, and each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted phenylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted dibenzofurylene , substituted or unsubstituted carbazolylene group.

Alternatively, the substituents in L, L ₁ and L ₂ are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl , trideuterated methyl, trimethylsilyl or phenyl.

In some embodiments, in the first compound, L is selected from the group consisting of a single bond or the following groups:

In some embodiments, in the first compound, L ₁ and L ₂ are the same or different, and each is independently selected from the group consisting of a single bond or the following groups:

In some embodiments, in the first compound, Identical or different, and each independently selected from the following groups:

In some embodiments, in the first compound, each _R1 is the same or different, and each is independently selected from deuterium, cyano, fluorine, trideuteratedmethyl, trimethylsilyl, trifluoromethyl, Cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl or carbazolyl.

In some embodiments, in the second compound, Z ₁ , Z ₂ and Z ₃ are the same or different, and each is independently selected from N or C(H), and at least two of Z ₁ to Z ₃ are N; or Z ₁ , Z ₂ and Z ₃ are all N.

More specifically, in some embodiments of the present application, in the first compound, X ₁ and X ₂ are both N, and X ₃ is C(H); or X ₁ and X ₃ are both N, and X ₂ is C (H); or, X ₂ and X ₃ are both N, and X ₁ is C(H); or, X ₁ , X ₂ , and X ₃ are all N.

In some embodiments, in Formula 2 When the group is selected from the structures shown in a-1 to a-3, the operating voltage of the device is lower.

In some embodiments, in the second compound, the group Selected from the structures shown in the following formulas a-17 to a-32:

Among them, T is O or S.

In some embodiments, the second compound has the following structures 2-1 to 2-9:

In some embodiments, in the second compound, Ar ₄ , Ar ₅ and Ar ₆ are each independently selected from the group consisting of carbon atoms having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39 or 40 or Unsubstituted aryl group with carbon atoms of 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40 substituted or unsubstituted heteroaryl groups.

In some embodiments, the substituents in Ar ₄ , Ar ₅ and Ar ₆ are each independently selected from deuterium, halogen groups, cyano groups, haloalkyl groups with 1 to 4 carbon atoms, and halogenated alkyl groups with 1 to 4 carbon atoms. Deuterated alkyl group, alkyl group with 1 to 4 carbon atoms, cycloalkyl group with 5 to 10 carbon atoms, aryl group with 6 to 15 carbon atoms, heteroaryl group with 5 to 12 carbon atoms group, a trialkylsilyl group with 3 to 8 carbon atoms or a deuterated aryl group with 6 to 15 carbon atoms. Optionally, any two adjacent substituents form a benzene ring or a fluorene ring.

In some embodiments, in the second compound, Ar ₄ , Ar ₅ and Ar ₆ are each independently selected from the substituted or unsubstituted group W ₂ ; the unsubstituted group W ₂ is selected from the following groups: Group:

The substituted group W ₂ has one or more substituents, and the substituents are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, and cyclopentyl. , cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuryl, dibenzothienyl, carbazolyl, benzox azolyl or benzothiazolyl, and when the number of substituents on group W ₂ is greater than 1, each substituent may be the same or different.

In some embodiments, in the second compound, Ar ₄ , Ar ₅ and Ar ₆ are the same or different, and each is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted Substituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carb Azolyl group, substituted or unsubstituted benzothiazolyl group, substituted or unsubstituted benzoxazolyl group, substituted or unsubstituted benzimidazolyl group.

Alternatively, the substituents in Ar ₄ , Ar ₅ and Ar ₆ are the same or different, and are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, Cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothienyl or carbazolyl, Optionally, in Ar ₄ and Ar ₅ , any two adjacent substituents form a benzene ring.

In some embodiments, in the second compound, Ar ₄ and Ar ₅ are the same or different, and each is independently selected from the following groups:

Ar ₆ is selected from the following groups:

In some embodiments, in the second compound, Ar ₄ and Ar ₅ are the same or different, and each is independently selected from the group consisting of:

In some embodiments, in the second compound, Ar ₆ is selected from the group consisting of:

In some embodiments, in the second compound, L ₃ , L ₄ and L ₅ are the same or different, and each is independently selected from the group consisting of single bonds and carbon atoms of 6, 7, 8, 9, 10, 11, 12, Substituted or unsubstituted arylene groups of 13, 14 or 15, substituted or unsubstituted arylene groups with carbon atoms of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 Substituted heteroarylene.

Optionally, the substituents in L ₃ , L ₄ and L ₅ are the same or different, and are each independently selected from deuterium, fluorine, cyano, alkyl with 1 to 5 carbon atoms, 3 to 5 carbon atoms. 8 trialkylsilyl group, fluoroalkyl group with 1 to 4 carbon atoms, deuterated alkyl group with 1 to 4 carbon atoms, phenyl or naphthyl group.

In some embodiments, in the second compound, L ₃ , L ₄ and L ₅ are the same or different, and each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, Substituted or unsubstituted biphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted phenylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazolylene group, substituted or unsubstituted pyridylene group, substituted or unsubstituted benzoxazolylene group, substituted or unsubstituted benzothiazolylene group.

Optionally, the substituents in L ₃ , L ₄ and L ₅ are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl base, trideuterated methyl, trimethylsilyl or phenyl.

In some embodiments, in the second compound, L ₃ is selected from the group consisting of a single bond or the following groups:

In some embodiments, in the second compound, L ₄ and L ₅ are the same or different, and each is independently selected from the group consisting of a single bond or the following groups:

In some embodiments, in the second compound, each R ₂ is the same or different, and each is independently selected from deuterium, cyano, fluorine, trideuterated methyl, trimethylsilyl, trifluoromethyl, cyclopentyl base, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl or carbazolyl.

In some embodiments, in the second compound, Identical or different, and each independently selected from the following groups:

In some embodiments, the first compound is selected from the following compounds represented by A-1 to A212:

This application also provides a light-emitting layer composition, which includes a first compound and a second compound, and the first compound has a structure shown in Formula 1:

Among them, Y is selected from S or O;

One of X ₁ and X ₂ is -N=, the other is O or S;

Ring A is selected from naphthalene ring or phenanthrene ring;

The second compound has the structure shown in Formula 2:

Groups in formula 2 Selected from the structures shown in a-1 to a-4,

One of U ₁ and U ₂ is -N=, the other is O or S; T is selected from O or S;

Each R ₂ is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with carbon atoms of 1 to 10, carbon number of Haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms , a heteroaryl group with 3 to 20 carbon atoms or a cycloalkyl group with 3 to 10 carbon atoms; n ₂ represents the number of R ₂ , and n ₂ is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

In some embodiments, the light-emitting layer composition includes a first compound and a second compound, and the mass ratio of the first compound to the second compound is 30:70˜70:30.

Optionally, the mass ratio of the first compound to the second compound in the light-emitting layer composition is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 30:70 to 70:30, Even more preferred is 40:60 to 60:40.

This application also provides the use of the composition in the light-emitting layer of an organic electroluminescent device.

The present application also provides organic electroluminescent devices comprising the composition.

The organic electroluminescent device provided by this application includes an anode and a cathode arranged oppositely, a cathode, anode and an organic layer. The organic layer includes an organic light-emitting layer including a first compound and a second compound.

Furthermore, the organic light-emitting layer includes a host material and a dopant. The host material includes a first compound and a second compound. Usually, based on the total weight of the two compounds, the mass ratio of the first compound to the second compound is 1:99 to 99:1, preferably 10:90 to 90:10, and further preferably 30:70 to 70: 30, more preferably 40:60 to 60:40.

In some embodiments, the mass ratio of the first compound (compound of formula 1) and the second compound (compound of formula 2) in the main body of the light-emitting layer of the organic electroluminescent device is 30:70 to 70:30.

Optionally, in the host material, the mass ratio of the first compound (compound of formula 1) and the second compound (compound of formula 2) is 35:65, 40:60, 45:55, 50:50, 55 :45, 60:40, 65:35.

In order to obtain a host material mixture, the first compound and the second compound may be placed in a oscillator and mixed to obtain a desired weight ratio of the mixture.

In order to form each layer constituting the organic electroluminescent device of the present application, dry film forming methods, such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film forming methods, such as inkjet printing, can be used , nozzle printing, slot coating, spin coating, dip coating, flow coating methods, etc.

Additionally, the first compound and the second compound may be film-formed in the methods listed above, typically by a co-evaporation method or a mixed evaporation method. Co-evaporation is a hybrid deposition method in which two or more materials are placed in respective single crucible sources and current is applied to multiple chambers simultaneously to evaporate the materials. Hybrid evaporation is a hybrid deposition method in which two or more materials are mixed in a crucible source prior to evaporation and an electrical current is applied to the chamber to evaporate the materials.

In some embodiments of the present application, the organic electroluminescent device is a phosphorescent device.

In some specific embodiments of the present application, the organic electroluminescent device is a green organic electroluminescent device or a red organic electroluminescent device.

In some ways of the present application, the organic electroluminescent device sequentially includes an anode (for example, ITO/Ag/ITO substrate), a hole transport layer, a hole adjustment layer, an organic light emitting layer, an electron transport layer, an electron injection layer, a cathode ( For example, Mg-Ag mixture) and organic coating. The hole transport layer is located between the anode and the organic light emitting layer, and the hole adjustment layer is located between the hole transport layer and the organic light emitting layer.

According to a specific implementation, as shown in Figure 1, the organic electroluminescent device includes an anode 100, a hole injection layer 310, a hole transport layer 321, and a hole adjustment layer (also known as a hole adjustment layer) stacked in sequence. auxiliary layer) 322, organic light-emitting layer 330, electron transport layer 340, electron injection layer 350 and cathode 200.

In this application, the anode 100 includes an anode material, which is preferably a material with a large work function that facilitates injection of holes into the functional layer. Specific examples of anode materials include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combined metals and oxides such as ZnO:Al or SnO ₂ :Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene ](PEDT), polypyrrole and polyaniline, but not limited thereto. Preferably, a transparent electrode including indium tin oxide (ITO) as an anode is included.

In this application, the hole transport layer or the hole adjustment layer may include one or more hole transport materials respectively. The hole transport layer materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types. The compound can be specifically selected from the compounds shown below or any combination thereof:

In one embodiment, hole transport layer 321 is composed of α-NPD or HT-5.

In one embodiment, hole regulating layer 322 is composed of HT-15 or HT-1.

Optionally, a hole injection layer 310 is also provided between the anode 100 and the hole transport layer 321 to enhance the ability to inject holes into the hole transport layer 321. The hole injection layer 310 can be made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not particularly limited in this application. The material of the hole injection layer 310 may, for example, be selected from the following compounds or any combination thereof;

In one embodiment of the present application, the hole injection layer 310 is composed of PD and α-NPD or PD and HT-5.

Alternatively, the organic light emitting layer 330 may include the host material and the guest material. Optionally, the organic light-emitting layer 330 is composed of a host material and a guest material. The holes injected into the organic light-emitting layer 330 and the electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons, and the excitons transfer energy to The host material transfers energy to the guest material, thereby enabling the guest material to emit light.

The host material of the organic light emitting layer 330 includes the first compound and the second compound.

The guest material of the organic light-emitting layer 330 can be a compound with a condensed aryl ring or its derivatives, a compound with a heteroaryl ring or its derivatives, an aromatic amine derivative or other materials, which is not specified in this application. limit. Guest materials are also called doping materials or dopants. According to the type of luminescence, it can be divided into fluorescent dopants and phosphorescent dopants. For example, specific examples of the phosphorescent dopant include, but are not limited to,

In one embodiment of the present application, the organic electroluminescent device is a red organic electroluminescent device. In a more specific implementation, the host material of the organic light-emitting layer 330 is composed of the first compound and the second compound. The guest material may be RD-1, for example.

In another embodiment, the organic electroluminescent device is a green organic electroluminescent device. In a more specific implementation, the host material of the organic light-emitting layer 330 is composed of the first compound and the second compound. The guest material may be fac-Ir(ppy) ₃ , for example.

The electron transport layer 340 may be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport materials may be selected from, but are not limited to, BmPyPhB, LiQ, benzimidazole derivatives, Electronic transport materials such as oxadiazole derivatives, quinoxaline derivatives, and triazine derivatives are not specifically limited in this application. The material of the electron transport layer 340 includes LiQ and other electrons. Sub-transport materials, the other electron transport materials can be selected from but not limited to the following compounds:

In one embodiment of the present application, the electron transport layer 340 is composed of ET-1 and LiQ or composed of ET-3 and LiQ.

In this application, the cathode 200 includes a cathode material, which is a material with a small work function that facilitates the injection of electrons into the functional layer. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; or multilayer materials such as LiF/Al , Liq/Al, LiO ₂ /Al, LiF/Ca, LiF/Al and BaF ₂ /Ca. Optionally, a metal electrode containing magnesium and silver is included as the cathode.

Optionally, an electron injection layer 350 is also provided between the cathode 200 and the electron transport layer 340 to enhance the ability of injecting electrons into the electron transport layer 340. The electron injection layer 350 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic substance. In one embodiment of the present application, the electron injection layer 350 includes ytterbium (Yb).

The present application not only provides the organic electroluminescent device including the compound represented by Formula 1 and the compound represented by Formula 2 for an organic light-emitting layer. The present application also provides an electronic device including the organic electroluminescent device of the present application.

According to one implementation, as shown in FIG. 2 , the electronic device provided is an electronic device 400 . The electronic device 400 may be, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices. For example, it may include but is not limited to a computer screen, a mobile phone screen, a television, electronic paper, emergency lighting, an optical module, etc.

The synthesis method of the first compound and the second compound of the present application will be specifically described below in conjunction with the synthesis examples, but the present application is not limited thereby.

Synthesis Example

Those skilled in the art will recognize that the chemical reactions described in this application can be used to suitably prepare many of the heterocyclic compounds of this application, and that other methods for preparing the compounds of this application are considered to be within the scope of this application. within. For example, the synthesis of non-exemplified compounds according to the present application can be successfully accomplished by one skilled in the art by modification methods, such as appropriately protecting interfering groups, by utilizing other known reagents in addition to those described herein, or by incorporating The reaction conditions were modified with some routine modifications. Compounds whose synthesis methods are not mentioned in this application are all raw material products obtained through commercial channels.

Synthesis of the first compound:

Synthesis of Sub-a1:

Under nitrogen atmosphere, add 7-bromo-2-phenylbenzoxazole (CAS: 1268137-13-8, 12.06g, 44 mmol), pinacol diborate (12.28g, 48.4mmol), potassium acetate (9.50g, 96.8mmol) and 1,4-dioxane (120mL), start stirring and heating, and wait until the system warms to 40°C , quickly add tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ , 0.40g, 0.44mmol) and 2-dicyclohexylphosphine-2',4',6'triisopropylbiphenyl ( XPhos, 0.42g, 0.88mmol), continue to raise the temperature to reflux, and stir the reaction overnight. After the system cools to room temperature, add 200 mL of water to the system, stir thoroughly for 30 minutes, filter under reduced pressure, wash the filter cake with deionized water until neutral, and then rinse with 100 mL of absolute ethanol to obtain a gray solid; use n-heptane for the crude product. The solution was pulped once with alkane, then dissolved with 200 mL of toluene and passed through a silica gel column. The filtrate was concentrated under reduced pressure to obtain a white solid Sub-a1 (10.17 g, yield 72%).

Synthesis of Sub-b1:

Under a nitrogen atmosphere, add Sub-a1 (17.66g, 55mmol), 7-bromo-1-iodo-2-hydroxynaphthalene (17.45g, 50mmol), tetrakis(triphenylphosphine)palladium ( Pd(PPh ₃ ) ₄ , 0.58g, 0.5mmol), anhydrous sodium carbonate (10.60g, 100mmol), toluene (180mL), absolute ethanol (45mL) and deionized water (45mL), start stirring and heating, and raise the temperature to reflux reaction for 16 hours. After the system was cooled to room temperature, it was extracted with dichloromethane (150 mL × 3 times). The organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to obtain white solid Sub-b1 (11.03 g, yield 53%).

Referring to the synthesis of Sub-a1, using reactant B shown in Table 1 instead of 7-bromo-1-iodo-2-hydroxynaphthalene, Sub-b2 to Sub-b5 were synthesized.

Table 1: Synthesis of Sub-b2 to Sub-b5

Synthesis of Sub-c1:

Under nitrogen atmosphere, add Sub-b1 (20.81g, 50mmol), tert-butyl peroxybenzoate (BzOOt-Bu, 19.42g, 100mmol), palladium acetate (1.12g, 5mmol), 3- Nitropyridine (0.62g, 5mmol), hexafluorobenzene (C ₆ F ₆ , 210mL) and N,N'-dimethylimidazolinone (DMI, 140mL), start stirring and heating, raise the temperature to 90°C and react for 4 hours . After the system was cooled to room temperature, it was extracted with ethyl acetate (100 mL × 3 times). The organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane/dichloromethane as the mobile phase to obtain white solid Sub-c1 (10.77g, yield 52%).

Refer to Sub-c1 and use reactant C shown in Table 2 instead of Sub-b1 to synthesize Sub-c2 to Sub-c5.

Table 2: Synthesis of Sub-c2 to Sub-c5

Synthesis of Sub-c6:

Under a nitrogen atmosphere, add Sub-c1 (10.36g, 25mmol) and 200mL benzene-D6 to a 100mL three-neck flask, heat it to 60°C, add trifluoromethanesulfonic acid (22.51g, 150mmol), and continue to heat it to boiling to stir the reaction. 24 hours. After the reaction system was cooled to room temperature, 50 mL of heavy water was added, stirred for 10 minutes, and then a saturated K ₃ PO ₄ aqueous solution was added to neutralize the reaction solution. The organic layer was extracted with dichloromethane (50 mL × 3 times), the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane/dichloromethane as the mobile phase to obtain white solid Sub-c6 (6.82g, yield 64%).

Synthesis of Sub-d1:

Under a nitrogen atmosphere, add Sub-c1 (13.36g, 50mmol), 2-chlorophenylboronic acid (8.60g, 55mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) _{4 )} to a 500mL three-necked flask in sequence. 0.58g, 0.5mmol), anhydrous sodium carbonate (10.60g, 100mmol), toluene (140mL), absolute ethanol (35mL) and deionized water (35mL), start stirring and heating, and heat to reflux for 16h. After the system was cooled to room temperature, it was extracted with dichloromethane (100 mL × 3 times). The organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to obtain white solid Sub-d1 (12.0 g, yield 54%).

Referring to the synthesis of Sub-d1, the reactant D shown in Table 3 is used to replace Sub-c1, and the reactant E is used to replace 2-chlorophenylboronic acid to synthesize Sub-d2.

Table 3: Synthesis of Sub-d2

Synthesis of Sub-e1:

Under nitrogen atmosphere, add Sub-c1 (18.23g, 44mmol), pinacol diborate (12.28g, 48.4mmol), potassium acetate (9.50g, 96.8mmol) and 1,4-diborate in sequence to a 500mL three-necked flask. Oxyhexanes (120 mL), start stirring and heating, wait until the system heats up to 40°C, quickly add tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ , 0.40g, 0.44mmol) and (2-dibenzylideneacetone). Cyclohexylphosphine-2',4',6'triiso Propylbiphenyl) (XPhos, 0.42g, 0.88mmol), continue to raise the temperature to reflux, and stir the reaction overnight. After the system cools to room temperature, add 200 mL of water to the system, stir thoroughly for 30 minutes, filter under reduced pressure, wash the filter cake with deionized water until neutral, and then rinse with 100 mL of absolute ethanol to obtain a gray solid; use n-heptane for the crude product. The mixture was slurried once with alkane, then dissolved with 200 mL of toluene and passed through a silica gel column to remove the catalyst. After concentration, a white solid (15.42 g, yield 76%) was obtained.

Refer to Sub-e1 and use the reactant F shown in Table 4 instead of Sub-c1 to synthesize Sub-e2 to Sub-e6.

Table 4: Synthesis of Sub-e2 to Sub-e6

Synthesis of compound A-2:

Under nitrogen atmosphere, add Sub-c1 (10.35g, 25mmol), RM-1 (CAS: 1290039-85-8, 9.22g, 27.5mmol), tris(dibenzylideneacetone)dipalladium (0.46g, 0.5mmol), (2-dicyclohexylphosphine-2',4',6'triisopropylbiphenyl) (Xphos, 0.48g , 1mmol), sodium tert-butoxide (4.80g, 50mmol) and xylene (xylene, 100mL), heat to reflux, stir and react overnight; after the system cools to room temperature, extract with dichloromethane (100mL×3 times), The organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to obtain white solid compound A-2 (8.0 g, yield 48%, m/z = 669.2 [M+H] ⁺ ).

Referring to the synthesis of compound A-2, using reactant G shown in Table 5 instead of Sub-c1 and reactant H instead of RM-1, the first compound (compound A-X) in Table 5 was synthesized.

Table 5: Synthesis of Compound AX

Synthesis of the second compound:

Synthesis of compound B-4:

Under a nitrogen atmosphere, add Sub-e1 (12.68g, 27.5mmol), CAS: 2401923-63-3 (8.72g, 25mmol), and tetrakis (triphenylphosphine) palladium (0.29g, 0.25 mmol), anhydrous sodium carbonate (5.3g, 50mmol), toluene (120mL), tetrahydrofuran (30mL) and deionized water (30mL), start stirring and heating, and heat to reflux for 16h. After the system was cooled to room temperature, it was extracted with dichloromethane (100 mL × 3 times). The organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to obtain a white solid, namely compound B-4 (11.82g, yield 73%; m/z=648.2[M+H] ⁺ ).

Referring to the synthesis of compound B-4, using reactant J shown in Table 6 instead of Sub-e1, and reactant K shown in Table 6 instead of CAS:2401923-63-3, the second compound (compounds B-X and C-X) in Table 6 was synthesized.

Table 6: Synthesis of compounds BX and CX

NMR characterization data of some compounds:

Compound A-2 NMR: ¹ H-NMR (400MHz, Methylene-Chloride-D2) δppm: 8.35 (d, 2H), 8.06 (d, 1H), 8.02-7.92 (m, 3H), 7.83 (d, 1H) ,7.75(d,1H),7.67-7.32(m,15H),7.16(s,1H),6.97(d,1H),6.92(d, 1H),6.71(d,2H);

Compound B-19 NMR: ¹ H-NMR (400MHz, Methylene-Chloride-D2) δppm: 9.68 (s, 1H), 8.84 (s, 2H), 8.79 (d, 2H), 8.65 (d, 1H), 8.35 (d,2H),8.24(d,1H),8.12(d,1H),8.09(s,1H),8.06(d,1H),7.75(d,1H),7.68-7.43(m,16H), 7.38(t.1H);

Compound C-45 NMR: ¹ H-NMR (400MHz, Methylene-Chloride-D2) δppm: 9.62 (s, 1H), 8.81 (s, 2H), 8.65 (d, 1H), 8.53 (d, 2H), 8.35 (d,2H),8.20-8.06(m,7H),8.02-7.93(m,4H),7.64(t,2H),7.57(t,2H),7.49(t,2H),7.36(t,1H ).

Preparation and evaluation of organic electroluminescent devices:

Example 1: Preparation of red organic electroluminescent device

First carry out anode pretreatment through the following process: in order of thickness: On the ITO/Ag/ITO substrate, UV ozone and O ₂ :N ₂ plasma are used for surface treatment to increase the work function of the anode, and organic solvents are used to clean the surface of the ITO substrate to remove impurities and oil stains on the surface of the ITO substrate.

On the experimental substrate (anode), PD:α-NPD was co-evaporated at a evaporation rate ratio of 2%:98% to form a thickness of hole injection layer (HIL), and then vacuum evaporate α-NPD on the hole injection layer to form a thickness of hole transport layer.

Compound HT-15 was vacuum evaporated on the hole transport layer to form a thickness of hole adjustment layer.

Next, on the hole adjustment layer, compound A-2 was used as the first host, compound B-4 was used as the second host, and RD-1 was used as the dopant, and a red light-emitting layer was prepared using a co-evaporation method. The first body: the second body: RD-1 are evaporated at the same time at a evaporation rate ratio of 50%: 50%: 2%, forming a thickness of red light emitting layer (EML).

On the light-emitting layer, compound ET-1 and LiQ are mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), Yb is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:8, and vacuum evaporated on the electron injection layer to form a thickness of the cathode.

In addition, the vacuum evaporation thickness on the above cathode is CP-1, thereby completing the fabrication of red organic electroluminescent devices.

Examples 2 to 30

An organic electroluminescent device was prepared using the same method as in Example 1, except that the combination of compounds A-2 and B-4 in Example 1 was replaced by the combination of the main body of the light-emitting layer in Table 7 when making the light-emitting layer.

Comparative examples 1 to 5

Among them, when preparing each embodiment and comparative example, the compound structure used is as follows:

The red organic electroluminescent devices prepared in Examples 1 to 30 and Comparative Examples 1 to 5 were tested for performance. Specifically, the IVL performance of the devices was tested under the condition of 10 mA/cm ^2. The T95 device life was at 20 mA/cm ² . The test was carried out under the conditions, and the test results are shown in Table 7.

Table 7

Referring to Table 7 above, it can be seen that the organic electroluminescent device of the present invention uses two specific compounds as the main materials of the light-emitting layer. Compared with the device of the comparative example, the luminous efficiency is increased by at least 12.1%, and the T95 life is increased by at least 12.1%. .

Example 31: Preparation of red organic electroluminescent device

On the experimental substrate (anode), PD:HT-5 was co-evaporated at a evaporation rate ratio of 2%:98% to form a thickness of hole injection layer (HIL), and then vacuum evaporate HT-5 on the hole injection layer to form a thickness of hole transport layer.

Compound HT-1 was vacuum evaporated on the hole transport layer to form a thickness of hole adjustment layer.

Next, on the hole adjustment layer, compound A-2 was used as the first host, compound B-9 was used as the second host, and RD-1 was used as the dopant, and a red light-emitting layer was prepared using a co-evaporation method. The first body and the second body are uniformly mixed according to a weight ratio of 50:50 to obtain a composition; the body composition: RD-1 is simultaneously evaporated at a evaporation rate ratio of 98%:3% to form a thickness of red light emitting layer (EML).

On the light-emitting layer, compound ET-3 and LiQ are mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), Yb is evaporated on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:8, and vacuum evaporated on the electron injection layer to form a thickness of the cathode.

Examples 32 to 39

An organic electroluminescent device was prepared using the same method as in Example 31, except that the combination of compounds A-2 and B-9 in Example 31 was replaced by the combination of the main body of the light-emitting layer in Table 8 when making the light-emitting layer.

Comparative Examples 6-7

The red organic electroluminescent devices prepared in Examples 31-39 and Comparative Examples 6-7 were tested for performance. Specifically, the IVL performance of the device was tested under the condition of 10mA/ ^cm2 . The T95 device life was at 20mA/ ^cm2 . The test was carried out under the conditions, and the test results are shown in Table 7.

Table 8

Referring to Table 8 above, it can be seen that the organic electroluminescent device of the present invention uses two specific compounds as the host materials of the light-emitting layer. Compared with the devices of Comparative Examples 6 and 7, the luminous efficiency is increased by at least 9.9%, and the T95 life is at least increased. 17.7%.

The preferred embodiments of the present invention are described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention. These simple modifications all belong to the protection scope of the present invention.

Claims

An organic electroluminescent device, including a cathode, an anode and an organic layer;

Wherein, the cathode and the anode are arranged oppositely;

The organic layer is located between the cathode and the anode;

The organic layer includes an organic light-emitting layer;

The organic light-emitting layer includes a first compound and a second compound;

The first compound has the structure shown in Formula 1:

Among them, Y is selected from S or O;

One of X 1 and X 2 is -N=, the other is O or S;

Ring A is selected from naphthalene ring or phenanthrene ring;

L, L 1 and L 2 are the same or different, and are each independently selected from a single bond, a substituted or unsubstituted arylene group with 6 to 30 carbon atoms, a substituted or unsubstituted group with 3 to 30 carbon atoms. heteroarylene;

Ar 1 , Ar 2 and Ar 3 are the same or different, and are each independently selected from a substituted or unsubstituted aryl group with 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group with 3 to 40 carbon atoms. ;

The substituents in L, L 1 , L 2 , Ar 1 , Ar 2 and Ar 3 are the same or different, and are each independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, Haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, 6 to 10 carbon atoms 20 aryl group, deuterated aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, 1 to 10 carbon atoms Alkoxy group, alkylthio group with 1 to 10 carbon atoms, aryloxy group with 6 to 20 carbon atoms or arylthio group with 6 to 20 carbon atoms; optionally, any two adjacent The substituents form a saturated or unsaturated 3 to 15-membered ring;

Each R 1 is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, halogenated alkyl group with 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Deuterated alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms or carbon Cycloalkyl group with 3 to 10 atoms; optionally, any two adjacent R 1s form a ring; n 1 represents the number of R 1s ; n 1 is selected from 0, 1, 2, 3, 4, and 5 , 6, 7, 8 or 9;

The second compound has the structure shown in Formula 2:

Wherein, Z 1 , Z 2 and Z 3 are each independently selected from N or C(H), and at least one of Z 1 to Z 3 is N;

Groups in formula 2 Selected from the structures shown in a-1 to a-4,

One of U 1 and U 2 is -N=, the other is O or S; T is selected from O or S;

L 3 , L 4 and L 5 are the same or different, and are each independently selected from single bonds, substituted or unsubstituted arylene groups with 6 to 30 carbon atoms, substituted or unsubstituted arylene groups with 3 to 30 carbon atoms. of heteroarylene;

Ar 4 , Ar 5 and Ar 6 are the same or different, and are each independently selected from a substituted or unsubstituted aryl group with 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group with 3 to 40 carbon atoms. ;

The substituents in L 3 , L 4 , L 5 , Ar 4 , Ar 5 and Ar 6 are the same or different, and are each independently selected from deuterium, cyano group, halogen group, and alkyl group with 1 to 10 carbon atoms. , haloalkyl group with 1 to 10 carbon atoms, deuterated alkyl group with 1 to 10 carbon atoms, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, 6 carbon atoms Aryl groups with ~20, deuterated aryl groups with 6 to 20 carbon atoms, heteroaryl groups with 3 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, 1 to 10 carbon atoms an alkoxy group, an alkylthio group with 1 to 10 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, or an arylthio group with 6 to 20 carbon atoms; optionally, any two adjacent The substituents form a saturated or unsaturated 3 to 15-membered ring;

Each R 2 is the same or different, and each is independently selected from deuterium, cyano group, halogen group, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms. 10 deuterated alkyl group, trialkylsilyl group with 3 to 12 carbon atoms, triphenylsilyl group, aryl group with 6 to 20 carbon atoms, heteroaryl group with 3 to 20 carbon atoms, or Cycloalkyl group with 3 to 10 carbon atoms; n 2 represents the number of R 2 , and n 2 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.
The organic electroluminescent device according to claim 1, wherein the group in Formula 1 Selected from the following structures shown in a-5 to a-16:

Among them, Y is O or S.
The organic electroluminescent device according to claim 1 or 2, wherein in Formula 1, Ar 1 , Ar 2 and Ar 3 are the same or different, and each is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted phenyl, Substituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted Substituted spirobifluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted diphenyl Furyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl;

Alternatively, the substituents in Ar 1 , Ar 2 and Ar 3 are the same or different, and are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, Cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothienyl or carbazolyl, Optionally, any two adjacent substituents in Ar 1 and Ar 2 form a benzene ring.
The organic electroluminescent device according to any one of claims 1 to 3, wherein in Formula 1, L, L 1 and L 2 are the same or different, and are each independently selected from single bonds, substituted or unsubstituted Phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted phenylene, substituted or unsubstituted dibenzo Thienyl, substituted or unsubstituted dibenzofurylene, substituted or unsubstituted carbazolylene;

Alternatively, the substituents in L, L 1 and L 2 are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl , trideuterated methyl, trimethylsilyl or phenyl.
The organic electroluminescent device according to any one of claims 1 to 4, wherein the first compound is selected from the following structures 1-2 to 1-8:
The organic electroluminescent device according to any one of claims 1 to 5, wherein in Formula 1, each R1 is the same or different, and each is independently selected from deuterium, cyano, fluorine, and trideuterated methyl. , trimethylsilyl, trifluoromethyl, cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, dibenzofuranyl, di Benzothienyl or carbazolyl.
The organic electroluminescent device according to any one of claims 1 to 6, wherein in formula 2, the group Selected from the following structures shown in a-17 to a-32:

Among them, T is O or S.
The organic electroluminescent device according to any one of claims 1 to 7, wherein in Formula 2, Ar 4 , Ar 5 and Ar 6 are the same or different, and each is independently selected from substituted or unsubstituted phenyl. , substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl , substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted Substituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl;

Alternatively, the substituents in Ar 4 , Ar 5 and Ar 6 are the same or different, and are each independently selected from deuterium, fluorine, cyano, trideuterated methyl, trimethylsilyl, trifluoromethyl, Cyclopentyl, cyclohexyl, adamantyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothienyl or carbazolyl, Optionally, in Ar 4 and Ar 5 , any two adjacent substituents form a benzene ring.
The organic electroluminescent device according to any one of claims 1 to 8, wherein in Formula 2, L 3 , L 4 and L 5 are the same or different, and are each independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted phenylene, substituted or unsubstituted diphenylene thienyl, substituted or unsubstituted dibenzofurylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted pyridylene, substituted or unsubstituted benzoxazolylene, substituted or unsubstituted Substituted benzothiazolyl;

Optionally, the substituents in L 3 , L 4 and L 5 are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl base, trideuterated methyl, trimethylsilyl or phenyl.
The organic electroluminescent device according to any one of claims 1 to 9, wherein in Formula 2, each R2 is the same or different, and each is independently selected from deuterium, cyano, fluorine, and trideuterated methyl. , trimethylsilyl, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, phenyl or naphthyl.
The organic electroluminescent device according to any one of claims 1 to 10, wherein the second compound is selected from the following structures 2-1 to 2-9:
The organic electroluminescent device according to any one of claims 1 to 11, wherein in the first compound, Identical or different, and each independently selected from the following groups:

Preferably, in the second compound, Each is independently selected from the following groups:
The organic electroluminescent device according to any one of claims 1 to 12, wherein the first compound is selected from the group consisting of the following compounds:

Preferably, the second compound is selected from the group consisting of:
An electronic device, characterized by including the organic electroluminescent device according to any one of claims 1 to 13.
A light-emitting layer composition comprising the first compound and the second compound according to any one of claims 1 to 13, the mass ratio of the first compound to the second compound being 30:70-70: 30.