CN112103395B

CN112103395B - Organic electroluminescent device and electronic apparatus

Info

Publication number: CN112103395B
Application number: CN202010948024.5A
Authority: CN
Inventors: 杨雷; 杨敏
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2020-08-10
Filing date: 2020-09-10
Publication date: 2022-11-15
Anticipated expiration: 2040-09-10
Also published as: CN112103395A; WO2022033280A1

Abstract

The present disclosure provides an organic electroluminescent device including an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode, which are sequentially stacked, wherein the hole transport layer includes a compound represented by chemical formula 1, and the organic light emitting layer includes a compound represented by chemical formula 4. The organic electroluminescent device can improve performance.

Description

Organic electroluminescent device and electronic apparatus

Technical Field

The present disclosure relates to the field of organic electroluminescence technologies, and in particular, to an organic electroluminescent device and an electronic apparatus.

Background

Organic electroluminescent devices, such as Organic Light Emitting Diodes (OLEDs), typically include a cathode and an anode disposed opposite each other, and a functional layer disposed between the cathode and the anode. The functional layer is composed of a plurality of organic or inorganic film layers and generally comprises an organic light-emitting layer, a hole transport layer positioned between the organic light-emitting layer and an anode, and an electron transport layer positioned between the organic light-emitting layer and a cathode. When voltage is applied to the anode and the cathode, the two electrodes generate an electric field, electrons on the cathode side move to the electroluminescent layer under the action of the electric field, holes on the anode side also move to the luminescent layer, the electrons and the holes are combined in the electroluminescent layer to form excitons, and the excitons are in an excited state and release energy outwards, so that the electroluminescent layer emits light outwards.

The above information disclosed in the background section is only for enhancement of understanding of the background of the present disclosure and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

The purpose of the present disclosure is to provide an organic electroluminescent device and an electronic apparatus, which improve the performance of the organic electroluminescent device.

In order to achieve the purpose, the technical scheme adopted by the disclosure is as follows:

according to a first aspect of the present disclosure, there is provided an organic electroluminescent device comprising an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode, which are sequentially stacked, wherein the hole transport layer comprises a compound represented by chemical formula 1, and the organic light emitting layer comprises a compound represented by chemical formula 4;

wherein, the first and the second end of the pipe are connected with each other,

represents a chemical bond;

a is a group represented by chemical formula 2;

x is C (R) ₃ R ₄ )，R ₃ And R ₄ Each independently selected from hydrogen and alkyl with 1-10 carbon atoms;

R ₁ and R ₂ The same or different, and are independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms;

n ₁ selected from 0, 1,2,3 or 4, when n is ₁ When not less than 2, any two R ₁ The same or different;

n ₂ selected from 0, 1,2,3 or 4, when n is ₂ When not less than 2, any two R ₂ The same or different;

n ₃ selected from 0, 1 or 2, when n ₃ When is equal to 2, two R ₃ Identical or different, two R ₄ The same or different;

l is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms;

l' is selected from substituted or unsubstituted arylene with 6-30 carbon atoms and substituted or unsubstituted heteroarylene with 3-30 carbon atoms;

Ar ₁ 、Ar ₃ each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;

Ar ₂ is a group represented by chemical formula 3;

Ar ₄ selected from hydrogen, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

l, L', ar ₁ 、Ar ₃ And Ar ₄ The substituents on the above groups are independently selected from deuterium, a halogen group, a cyano group, a heteroaryl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, and a phosphonoxy group having 6 to 18 carbon atoms.

According to a second aspect of the present disclosure, there is provided an electronic apparatus comprising the above organic electroluminescent device.

Drawings

The above and other features and advantages of the present application will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.

Fig. 1 is a schematic structural view 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.

The reference numerals of the main elements in the figures are as follows:

100. an anode; 200. a cathode; 310. a hole injection layer; 321. a hole transport layer; 322. an electron blocking layer; 330. an organic light-emitting layer; 340. an electron transport layer; 350. an electron injection layer; 400. an electronic device.

Detailed Description

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different 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 concept of example embodiments 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 give a thorough understanding of embodiments of the disclosure.

In the drawings, the thickness of regions and layers may be exaggerated for clarity. The same reference numerals in the drawings denote the same or similar structures, and thus a detailed description thereof will be omitted.

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 give a thorough understanding of embodiments of the disclosure. One skilled in the relevant art will recognize, however, that the embodiments of the disclosure can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring major technical ideas of the disclosure.

In the context of the present application, it is,

and

as used herein, the term "substituent" refers to a position bonded to another substituent or a bonding position.

In this application, the number of carbon atoms of a group refers to all the number of carbon atoms. For example, in a substituted arylene group having 10 carbon atoms, all of the carbon atoms of the arylene group and the substituents thereon are 10. Illustratively, the 9, 9-dimethylfluorenyl group is a substituted aryl group having 15 carbon atoms.

In the present application, when a specific definition is not otherwise provided, "hetero" means that at least 1 hetero atom of B, N, O, S, se, si, or P, etc. is included in one functional group and the remaining atoms are carbon and hydrogen. An unsubstituted alkyl group can be a "saturated alkyl group" without any double or triple bonds.

The description adopted in the application is that each of \8230, \8230, independently and '8230, and \8230, independently and respectively, are selected from' interchangeable, should be broadly understood, and can mean that specific options expressed between the same symbols in different groups do not affect each other, or that specific options expressed between the same symbols in the same groups do not affect each other. For example: in "

Wherein each q is independently 0, 1,2 or 3, and each R "is independently selected from the group consisting of hydrogen, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' exist on a benzene ring, each R ' can be the same or different, and the options of each R ' do not influence each other; the formula Q-2 represents that each benzene ring of biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on the two benzene rings can be the same or different, each R 'can be the same or different, and the options of each R' are not influenced with each other.

In the present application, the term "substituted or unsubstituted" means either no substituent or substituted with one or more substituents. Such substituents include, but are not limited to, deuterium, halogen groups (F, cl, br), cyano, alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, aryloxy, arylthio, silyl, alkylamino, cycloalkyl, heterocyclyl.

In this application, "optional" or "optionally" means that the subsequently described event or circumstance can, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "optionally, two substituents attached to the same atom are linked to each other to form a saturated or unsaturated 5-to 18-membered aliphatic ring or a 5-to 18-membered aromatic ring with the atoms to which they are commonly attached" means: when two substituents are bonded to the same atom, the two substituents may be present independently of each other, or may be bonded to each other so as to form a saturated or unsaturated 5-to 18-membered aliphatic ring or a 5-to 18-membered aromatic ring with the atom to which they are bonded together.

In the present application, "alkyl" may include straight chain alkyl or branched alkyl. Alkyl groups may have 1 to 20 carbon atoms, and numerical ranges such as "1 to 20" refer herein to each integer in the given range; for example, "1 to 20 carbon atoms" refers to an alkyl group that may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. The alkyl group can also be a medium size alkyl group having 1 to 10 carbon atoms. The alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. In still other embodiments, the alkyl group contains 1 to 4 carbon atoms; in still other embodiments, the alkyl group contains 1 to 3 carbon atoms. The alkyl group may be optionally substituted with one or more substituents described herein. Examples of alkyl groups include, but are not limited to, methyl (Me, -CH) ₃ ) Ethyl group (Et, -CH) ₂ CH ₃ ) N-propyl (n-Pr, -CH) ₂ CH ₂ CH ₃ ) Isopropyl group (i-Pr, -CH (CH) ₃ ) ₂ ) N-butyl (n-Bu, -CH) ₂ CH ₂ CH ₂ CH ₃ ) Isobutyl (i-Bu, -CH) ₂ CH(CH ₃ ) ₂ ) Sec-butyl (s-Bu, -CH (CH) ₃ )CH ₂ CH ₃ ) Tert-butyl (t-Bu, -C (CH) ₃ ) ₃ ) And so on. Further, the alkyl group may beSubstituted or unsubstituted.

In this application, "alkenyl" refers to a hydrocarbon group that contains one or more double bonds in a straight or branched hydrocarbon chain. Alkenyl groups may be unsubstituted or substituted. Alkenyl groups may have 1 to 20 carbon atoms, and whenever appearing herein, numerical ranges such as "1 to 20" refer to each integer in the given range; for example, "1 to 20 carbon atoms" refers to an alkenyl group that may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. For example, the alkenyl group can be vinyl, butadiene, or 1,3, 5-hexatriene.

In this application, cycloalkyl refers to cyclic saturated hydrocarbons, including monocyclic and polycyclic structures. Cycloalkyl groups may have 3-20 carbon atoms, a numerical range such as "3 to 20" refers to each integer in the given range; for example, "3 to 20 carbon atoms" refers to a cycloalkyl group that can contain 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. The cycloalkyl group may be a small ring, a normal ring or a large ring having 3 to 20 carbon atoms. Cycloalkyl groups can also be divided into monocyclic-only one ring, bicyclic-two rings-or polycyclic-three or more rings. Cycloalkyl groups can also be divided into spiro rings, fused rings, and bridged rings, in which two rings share a common carbon atom, and more than two rings share a common carbon atom. In addition, cycloalkyl groups may be substituted or unsubstituted. In some embodiments cycloalkyl is 5 to 10 membered cycloalkyl, in other embodiments cycloalkyl is 5 to 8 membered cycloalkyl, examples of which may be, but are not limited to: five-membered cycloalkyl, i.e., cyclopentyl, six-membered cycloalkylcyclohexylalkyl, 10-membered polycycloalkyl such as adamantyl, and the like.

In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused ring aryl group, two or more monocyclic aryl groups connected by carbon-carbon bond conjugation, a monocyclic aryl group and a fused ring aryl group connected by carbon-carbon bond conjugation, two or more fused ring aryl groups connected by carbon-carbon bond conjugation. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as an aryl group in the present application. Wherein the aryl group does not contain a hetero atom such as B, N, O, S, se, si or P. For example, biphenyl, terphenyl, and the like are aryl groups in this application. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, hexabiphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, perylenyl, benzofluoranthenyl, pyrenyl, perylene,

A phenyl group, a 9,9 dimethylfluorenyl group, a 9,9 diphenylfluorenyl group, a spirobifluorenyl group, an indenyl group and the like, without being limited thereto.

In this application, substituted aryl refers to an aryl in which one or more hydrogen atoms are replaced with another group. For example, at least one hydrogen atom is substituted with a deuterium atom, F, cl, I, CN, hydroxyl, amino, branched alkyl, linear alkyl, cycloalkyl, alkoxy, alkylamino, alkylthio, aryl, heteroaryl, or other group. Specific examples of heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl, dibenzothiophene-substituted phenyl, pyridine-substituted phenyl, and the like. Specific examples of aryl-substituted aryl groups include, but are not limited to, naphthyl-substituted phenyl, phenyl-substituted naphthyl, phenyl-substituted phenanthryl, and the like. It is understood that the number of carbon atoms of the substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group. For example, a substituted aryl group having 18 carbon atoms means that the total number of carbon atoms of the aryl group and the substituent on the aryl group is 18. For example, 9-dimethylfluorenyl is a substituted aryl group having 15 carbon atoms.

In the present application, the heteroaryl group may be a heteroaryl group including at least one of B, O, N, P, si, se, and S as a heteroatom. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring, and any one of the aromatic ring systems contains the heteroatom. The term "heteroaryl" as used herein may include 1,2,3,4, 5,6,7,8, 9 or 10 heteroatoms selected from any of B, O, N, P, si, se and S, and may have from 3 to 40 carbon atoms, in some embodiments from 3 to 30 carbon atoms, and in other embodiments from 3 to 20, or from 3 to 18, or from 3 to 12, or from 12 to 18, or from 3 to 20 carbon atoms. For example, the number of carbon atoms of the heteroaryl group can be 3,5, 6,7,8, 9,10, 11, 12, 13, 14, 15, 16, 18, 20 or 40, and of course, other numbers are also possible and are not listed here.

Exemplary heteroaryl groups may include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-arylcarbazolyl (e.g., N-phenylcarbazolyl), N-heteroarylcarbazolyl (e.g., N-pyridylcarbazyl), N-alkylcarbazolyl (e.g., N-methylcarbazyl), and the like. Wherein, thienyl, furyl, phenanthroline group and the like are heteroaryl of a single aromatic ring system type, and N-aryl carbazolyl and N-heteroaryl carbazolyl are heteroaryl of a polycyclic system type connected by carbon-carbon bond conjugation.

In the present application, the heteroaryl group having 3 to 18 ring-forming carbon atoms means that the number of carbon atoms in the heteroaryl group located on the heteroaryl ring is 3 to 18, and the number of carbon atoms in the substituent on the heteroaryl group is not counted. The number of carbon atoms in the heteroaryl group may be 3 to 18, 3 to 12, or 3 to 8, but is not limited thereto.

In this application, the explanation for aryl applies to arylene, the explanation for heteroaryl applies equally to heteroarylene, the explanation for alkyl applies to alkylene, and the explanation for cycloalkyl applies to cycloalkylene.

In the present invention, the ring system formed by n atoms is an n-membered ring. For example, phenyl is a 6-membered aryl. The 6-to 10-membered aromatic ring means a benzene ring, an indene ring, a naphthalene ring and the like.

The "ring" in the present application includes saturated rings, unsaturated rings; saturated rings, i.e., cycloalkyl, heterocycloalkyl, unsaturated rings, i.e., cycloalkenyl, heterocycloalkenyl, aryl, and heteroaryl.

An delocalized bond in the present application refers to a single bond extending from a ring system

Or

It means that one end of the linkage may be attached to any position in the ring system through which the linkage runs, and the other end to the rest of the compound molecule. For example, as shown in the following formula (X), naphthyl represented by the formula (X) is connected to other positions of the molecule through two non-positioned connecting bonds penetrating through a double ring, and the meaning of the naphthyl represented by the formula (X-1) to the formula (X-10) includes any possible connecting mode shown in the formula (X-1).

For example, as shown in the following formula (X '), the phenanthryl group represented by the formula (X') is bonded to the rest of the molecule via an delocalized bond extending from the middle of the benzene ring on one side, and the meaning of the phenanthryl group includes any of the possible bonding modes as shown in the formulas (X '-1) to (X' -4).

An delocalized substituent, as used herein, refers to a substituent attached by a single bond extending from the center of the ring system, meaning that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R group represented by the formula (Y) is bonded to the quinoline ring through an delocalized bond, and the meaning thereof includes any possible bonding manner as shown in the formulae (Y-1) to (Y-7).

In the related art, the performance of the organic electroluminescent device is generally optimized by individually optimizing the hole transport layer material. When the hole transport layer material has a shallower HOMO level through the structural adjustment, the driving voltage of the organic electroluminescent device may be generally reduced, but the phenomenon of reduction in the light emitting efficiency of the organic electroluminescent device is often accompanied. When the hole transport layer material has a deeper HOMO level through structural adjustment, the light emitting efficiency of the organic electroluminescent device can be generally improved, but the driving voltage of the organic electroluminescent device tends to increase. Therefore, optimization of organic electroluminescent devices often requires a balance between driving voltage and luminous efficiency, making it difficult to improve both simultaneously, or to improve one without significant disadvantages to the other.

As shown in fig. 1, the present disclosure provides an organic electroluminescent device comprising 100 an anode, a hole transport layer 321, an organic light emitting layer 330, an electron transport layer 340, and a cathode 200, which are sequentially stacked, wherein the hole transport layer 321 comprises a compound of formula 1, and the organic light emitting layer 330 comprises a compound of formula 4;

wherein the content of the first and second substances,

represents a chemical bond;

a is a group represented by chemical formula 2;

x is C (R) ₃ R ₄ )，R ₃ And R ₄ Each independently selected from hydrogen and alkyl groups having 1 to 10 carbon atoms;

n ₁ selected from 0, 1,2,3 or 4, when n ₁ When not less than 2, any two R ₁ The same or different;

n ₂ selected from 0, 1,2,3 or 4, when n is ₂ When greater than or equal to 2, any two R ₂ The same or different;

n ₃ selected from 0, 1 or 2, when n ₃ When equal to 2, two R ₃ Identical or different, two R ₄ The same or different;

l is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms;

Ar ₂ is a group represented by chemical formula 3;

Ar ₄ selected from hydrogen, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 3 to 30 carbon atomsUnsubstituted heteroaryl;

the L, L', ar ₁ 、Ar ₃ And Ar ₄ The substituents on the above groups are independently selected from deuterium, a halogen group, a cyano group, a heteroaryl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, and a phosphonoxy group having 6 to 18 carbon atoms.

The compound shown in chemical formula 1 is used as a hole transport layer of the organic electroluminescent device, and the compound shown in chemical formula 4 is used as a main material of an organic light-emitting layer of the organic electroluminescent device, so that at least one aspect of the luminous efficiency and the service life of the organic electroluminescent device can be improved, the driving voltage, the luminous efficiency and the service life of the organic electroluminescent device are not sacrificed, and the performance of the organic electroluminescent device is improved.

Preferably, the compound of formula 1 is selected from the group consisting of the following formulae:

alternatively, R ₁ And R ₂ The same or different, and each is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

Preferably, R ₁ And R ₂ Identical or different and are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl.

Preferably, R ₁ And R ₂ The same or different, and are respectively and independently selected from methyl, ethyl, n-propyl and tert-butyl, or selected from the group consisting of substituents shown as R-A, R-B, R-C, R-D, R-E and R-F:

preferably, R ₁ And R ₂ Are respectively selected from isopropyl and tert-butyl.

Alternatively, R ₃ And R ₄ The same or different, and each is independently selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

Preferably, R ₃ And R ₄ Identical or different and are each independently selected from hydrogen, methyl, ethyl, propyl, tert-butyl, phenyl, biphenyl, naphthyl.

Preferably, R ₃ And R ₄ The same is true.

Preferably, when n ₃ When =1, R ₃ And R ₄ Identical and are all methyl; when n is ₃ When =2, R ₃ And R ₄ Are identical and are all hydrogen.

Alternatively, L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms.

Alternatively, the substituent of L is selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, pyridyl, carbazolyl, dibenzofuran, dibenzothienyl.

Alternatively, L is selected from a single bond or a group of formula j-1 through formula j-6:

wherein M is ₂ Selected from a single bond or

E ₁ ～E ₁₀ Each independently selected from: deuterium, a halogen group, a cyano group, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, a phosphonoxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms;

e _r is a substituent E _r R is any integer from 1 to 10; when r is selected from 1,2,3,4, 5,6, e _r Selected from 0, 1,2,3 or 4; when r is 7, e _r Selected from 0, 1,2,3,4, 5 or 6; when r is 10, e _r Selected from 0, 1,2,3 or 4; when r is selected from 8 or 9, e _r Selected from 0, 1,2,3,4, 5,6,7 or 8; when e is _r When greater than 1, any two of E _r The same or different.

Preferably, E in the formulae j-1 to j-6 ₁ ～E ₁₀ Each independently selected from: deuterium, fluorine, cyano, trimethylsilyl, dimethylphenylsilyl, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropyl, cyclohexyl, cyclopentyl, phenyl, biphenyl, naphthyl.

Preferably, L is selected from a single bond or a group of formula j-1 to formula j-6, the total number of carbon atoms of the groups of formula j-1 to formula j-6 is not more than 18.

Preferably, L is selected from a single bond or the group consisting of:

preferably, L is selected from a single bond or a group consisting of groups represented by L-A, L-B, L-C, L-D, L-E, L-F, L-G, L-H, L-I, L-J, and L-K:

* Is represented by

Is connected with

Is/are as follows

And (4) connecting.

Alternatively, ar ₁ 、Ar ₃ Each independently selected from substituted or unsubstituted aryl groups having 6 to 20 carbon atoms;

Ar ₄ selected from hydrogen and substituted or unsubstituted aryl with 6-20 carbon atoms.

Preferably, ar ₁ 、Ar ₃ Each independently selected from the group consisting of substituents represented by formula i-1 to formula i-11;

Ar ₄ selected from hydrogen, substituents of formula i-1 to formula i-11:

wherein M is ₁ Selected from a single bond or

H ₁ ～H ₂₁ Each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, carbonAn alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a heterocycloalkyl group having 2 to 10 carbon atoms; h ₄ ～H ₂₀ Any one of them may be independently selected from aryl groups having 6 to 20 carbon atoms;

h _k is a substituent H _k K is any integer from 1 to 21; wherein, when k is selected from 5 or 17, h _k Selected from 1,2 or 3; when k is selected from 2, 7,8, 12, 15, 16, 18 or 21, h _k Selected from 1,2,3 or 4; when k is selected from 1,3, 4, 6, 9 or 14, h _k Selected from 1,2,3,4 or 5; when k is 13, h _k Selected from 1,2,3,4, 5 or 6; when k is selected from 10 or 19, h _k Selected from 1,2,3,4, 5,6 or 7; when k is selected from 20, h _k Selected from 1,2,3,4, 5,6,7 or 8; when k is 11, h _k Selected from 1,2,3,4, 5,6,7,8 or 9; when h is generated _k When greater than 1, any two H _k The same or different; optionally, any two adjacent R _k Are connected with each other to form a ring;

K ₁ selected from O, S, se, N (H) ₂₂ )、C(H ₂₃ H ₂₄ )、Si(H ₂₃ H ₂₄ ) (ii) a Wherein H ₂₂ 、H ₂₃ 、H ₂₄ Each independently selected from: an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms;

K ₂ selected from single bond, O, S, se, N (H) ₂₅ )、C(H ₂₆ H ₂₇ )、Si(H ₂₆ H ₂₇ ) (ii) a Wherein H ₂₅ 、H ₂₆ 、H ₂₇ Each independently selected from: an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms.

Preferably, the total number of carbon atoms of the substituents represented by the above formulas i-1 to i-11 is not more than 20.

Preferably, H ₁ ～H ₂₁ Each independently selected from: deuterium, fluoro, cyano, trimethylsilyl, dimethylphenylsilyl, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropyl, cyclohexyl, cyclopentyl. H ₄ ～H ₂₀ Any of which may also be independently selected from phenyl, biphenyl, naphthyl.

Preferably, ar ₁ Selected from the group consisting of:

preferably, ar ₁ Selected from the group consisting of I-A, I-B, I-C, I-D, I-E, I-F, I-G, I-H, I-I, I-J, I-K, I-L, I-M, I-N:

preferably, the nitrogen-containing compound is selected from the group formed by:

wherein when n is ₃ When =0, the structural formula of chemical formula 1 is

When n is ₃ ＝1，R ₃ 、R ₄ When it is methyl, the structural formula of chemical formula 1 is

When n is ₃ =2, and R ₃ And R ₄ When simultaneously hydrogen, the structural formula of chemical formula 1 is

"-" indicates that R is absent at the 1,2,3, 4-position of chemical formula 1 ₁ Substituted, "- -" indicates that the 5,6,7, 8-position of chemical formula 1 has no R ₂ Substitution;

R-A, R-B, R-C, R-D, R-E and R-F represent R with different structures ₁ Or R ₂ And each corresponds to the group shown below;

L-A, L-B, L-C, L-D, L-E, L-F, L-G, L-H, L-I, L-J, L-K represent L of different structures and respectively correspond to the groups shown as follows:

* Is represented by

Is connected with

Is/are as follows

Connecting;

I-A, I-B, I-C, I-D, I-E, I-F, I-G, I-H, I-I, I-J, I-K, I-L, I-M, I-N represent Ar with different structures ₁ And each corresponds to the group shown below

Preferably, ar ₃ Selected from the group consisting of:

alternatively, the hole transport layer is composed of the compound represented by chemical formula 1.

Preferably, ar ₃ Selected from the group consisting of:

preferably, ar ₄ Selected from hydrogen, phenyl, naphthyl, phenanthryl, anthryl and pyrenyl.

Preferably, ar ₄ Selected from hydrogen,

Alternatively, L' is selected from the group consisting of groups represented by formula j-1 through formula j-10:

wherein M is ₂ Selected from a single bond or

E ₁ ～E ₁₅ Each independently selected from: deuterium, a halogen group, a cyano group, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, a phosphonooxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms;

e _t is a substituent E _t T is any integer from 1 to 15; when t is selected from 11 and 12, e _t Selected from 0, 1,2 or 3; when t is selected from 1,2,3,4, 5,6, 10, e _t Selected from 0, 1,2,3 or 4; when t is selected from 13, 14 and 15, e _t Selected from 0, 1,2,3,4 or 5; when t is 7, e _t Selected from 0, 1,2,34, 5 or 6; when t is selected from 8 or 9, e _t Selected from 0, 1,2,3,4, 5,6,7 or 8; when e is _t When greater than 1, any two of E _t The same or different;

y is selected from C (R) ₅ R ₆ )、Si(R ₇ R ₈ )、O、S、Se、N(R ₉ ) (ii) a Wherein R is ₅ To R ₉ Each independently selected from: an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms.

When L' is selected from the group consisting of the groups represented by the formulas j-1 to j-10, the number of carbon atoms of the groups represented by the formulas j-1 to j-10 is not more than 30.

Based on the difference of L ', the compound of chemical formula 4 of the present disclosure may specifically include D-type compounds and E-type compounds, wherein L' of the D-type compounds is selected from the group consisting of the groups of chemical formula j-1, chemical formula j-2, chemical formula j-3, chemical formula j-4, chemical formula j-5, and chemical formula j-6; l' of the E-type compound is selected from the group consisting of the groups represented by the above chemical formula j-7, chemical formula j-8, chemical formula j-9 and chemical formula j-10.

Preferably, L' is selected from the group consisting of:

preferably, L' of the D-type compound is selected from

Preferably, L' of the E-class compound is selected from

Preferably, L' is selected from the group consisting of:

wherein, # is used to indicate L' and

the site of attachment, # # is used to denote L' and Ar ₄ The site of attachment.

Preferably, L' of the class D compound is selected from:

preferably, L' of the E-class compound is selected from:

preferably, the first and second electrodes are formed of a metal,

selected from the group consisting of:

preferably, of compounds of class D

Selected from the group consisting of:

preferably of compounds of the E class

Selected from the group consisting of:

preferably, the compound represented by chemical formula 4 is selected from the group consisting of:

wherein, the D-type compound can comprise a compound D-1 to a compound D-31; the class E compounds may include compounds E-1 through E-42.

Alternatively, the organic light emitting layer 330 may further include a guest material, and the host material and the guest material are uniformly mixed. The holes injected into the organic light emitting layer 330 and the electrons injected into the organic light emitting layer 330 may be recombined in the organic light emitting layer 330 to form excitons, the excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.

Preferably, the organic electroluminescent device further comprises a hole injection layer 310 disposed between the anode 100 and the hole transport layer 321; the hole injection layer 310 includes a compound of chemical formula 1 and a compound of chemical formula 5;

wherein Ar is ₅ 、Ar ₆ 、Ar ₇ Each independently selected from substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms;

Ar ₅ 、Ar ₆ 、Ar ₇ the substituents are respectively and independently selected from fluorine, chlorine, bromine, cyano-group, trifluoromethyl and nitro, and any two substituents are the same or different.

Alternatively, ar ₅ 、Ar ₆ 、Ar ₇ Each independently selected from substituted aryl groups having 6 to 30 carbon atoms and pyridyl groups.

Preferably, ar ₅ 、Ar ₆ 、Ar ₇ Each independently selected from substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted phenanthryl, substituted fluorenyl, substituted pyridyl.

Preferably, ar ₅ 、Ar ₆ 、Ar ₇ The substituents on the above are respectively and independently selected from fluorine, cyano and trifluoromethyl.

Preferably, ar is ₅ 、Ar ₆ 、Ar ₇ Are all completely substituted.

Preferably, ar ₅ 、Ar ₆ 、Ar ₇ Each independently selected from tetrafluoropyridyl, tetrafluoro- (trifluoromethyl) phenyl, cyano-tetrafluorophenyl, dichloro-difluoro- (trifluoromethyl) phenyl, pentacyanophenyl, penta (trifluoromethyl) phenyl, tetracyanopyridyl, tetra (trifluoromethyl) pyridyl.

In one embodiment of the present disclosure, the compound of chemical formula 5 is a compound represented by the following PD:

optionally, the organic electroluminescent device further comprises an electron blocking layer, wherein the electron blocking layer is arranged between the hole transport layer and the organic light emitting layer; the electron blocking layer includes a compound represented by chemical formula 6:

wherein R is ₁₀ And R ₁₁ The same or different, and are respectively and independently selected from deuterium, fluorine, alkyl with 1-10 carbon atoms, cycloalkyl with 5-10 carbon atoms, trialkylsilyl with 3-10 carbon atoms, cyano, aryl with 6-20 carbon atoms, heteroaryl with 3-20 carbon atoms, alkoxy with 1-10 carbon atoms and alkylthio with 1-10 carbon atoms;

L ₁ and L ₂ The same or different, each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; and L is ₁ And L ₂ Not being a single bond at the same time;

Ar ₈ and Ar ₉ Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms;

n ₄ is R ₁₀ And is selected from 0, 1,2,3 or 4; when n is ₄ When greater than or equal to 2, any two R ₁₀ The same or different;

n ₅ is R ₁₁ And is selected from 0, 1,2,3 or 4; when n is ₅ When not less than 2, any two R ₁₁ The same or different.

Further, when n is ₄ When not less than 2, any one R ₁₀ Selected from deuterium, fluorine, cyano, alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 3 to 12 carbon atoms, alkoxy having 1 to 3 carbon atoms, and alkylthio having 1 to 3 carbon atomsAnd (4) a base.

Preferably, R ₁₀ Selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, cyclopentyl, cyclohexyl, adamantyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl.

Further, when n is ₅ When not less than 2, any one R ₁₁ Selected from deuterium, fluorine, cyano, alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 3 to 12 carbon atoms, alkoxy having 1 to 3 carbon atoms and alkylthio having 1 to 3 carbon atoms.

Preferably, R ₁₁ Selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, cyclopentyl, cyclohexyl, adamantyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl.

Further, L ₁ Selected from the group consisting of a single bond, phenylene, biphenylene, naphthylene, dibenzofuranylene, dibenzothiophenylene.

Further, L ₂ Selected from the group consisting of a single bond, phenylene, biphenylene, naphthylene, dibenzofuranylene, dibenzothiophenyl.

Further, ar ₈ Selected from phenyl, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothienyl, anthryl, phenanthryl and pyrenyl.

Further, ar ₉ Selected from phenyl, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothienyl, anthryl, phenanthryl, pyrenyl.

Alternatively, the compound represented by chemical formula 6 is selected from the group consisting of:

alternatively, the hole injection layer 310 is composed of the compound of chemical formula 1 and the compound of chemical formula 4, which are uniformly mixed.

Optionally, the anode 100 comprises an anode material, which may be selected to be a material with a large work function that facilitates hole injection into the functional layer. Specific examples of anode materials include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO: al or SnO ₂ Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole and polyaniline. Optionally including a transparent electrode comprising Indium Tin Oxide (ITO) as the anode.

Alternatively, the electron transport layer 340 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials selected from, but not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials.

Alternatively, the cathode 200 may comprise a cathode material, which is a material with a small work function that facilitates electron injection 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 a multilayer material such as LiF/Al, liq/Al, liO ₂ Al, liF/Ca, liF/Al and BaF ₂ and/Ca. A metal electrode comprising aluminum may optionally be included as a cathode. In one embodiment of the present application, the material of the cathode 200 may be a magnesium silver alloy.

Optionally, the organic electroluminescent device may further include an electron blocking layer 322, and the electron blocking layer 322 is disposed between the hole transport layer 321 and the organic light emitting layer 330.

Preferably, the HOMO level of the material of the electron blocking layer 322 is deeper (i.e., the HOMO absolute value is larger) than that of the compound shown in chemical formula 1, and shallower than that of the compound shown in chemical formula 4. In this way, the energy barrier between the hole transport layer and the organic light emitting layer can be further reduced, and the efficiency of injecting holes into the organic light emitting layer can be improved. This can reduce the driving voltage of the organic electroluminescent device or improve the light emitting efficiency of the organic electroluminescent device. In particular, in some embodiments, the electron blocking layer may further balance electrons and holes injected into the organic light emitting layer, which may help to improve the light emitting efficiency and lifetime of the organic electroluminescent device.

Preferably, the LUMO level of the electron blocking layer material is shallower (i.e., the LUMO absolute value is smaller) than that of the compound represented by chemical formula 4. The electron blocking layer can inhibit the migration of electrons from the organic light emitting layer to the hole transport layer, so that the electrons are blocked in the organic light emitting layer as much as possible, on one hand, the exciton output in the organic light emitting layer can be improved, and on the other hand, the impact of the electrons on the hole transport layer material can be avoided. Therefore, the luminous efficiency and the service life of the organic electroluminescent device are improved conveniently. Further preferably, the LUMO level of the electron blocking layer material is different from the LUMO level of the compound represented by chemical formula 4 by 0.5eV.

In one embodiment of the present disclosure, the material of the electron blocking layer may be of the structure shown in EB-1:

optionally, an electron injection layer 350 may be further disposed between the cathode 200 and the electron transport layer 340 to enhance the ability to inject 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 material. For example, the electron injection layer 350 may include LiQ.

As shown in fig. 2, the present disclosure also provides an electronic device 400, where the electronic device 400 includes any one of the organic electroluminescent devices described in the above organic electroluminescent device embodiments. The electronic device 400 may be a smart watch, smart phone, laptop computer, television, computer screen, electronic paper, lights, AR (augmented reality) glasses, VR (virtual reality) helmet, or other type of electronic device 400. Since the electronic device 400 has any one of the organic electroluminescent devices described in the above embodiments of the organic electroluminescent device, the same advantages are obtained, and the details of the disclosure are not repeated herein.

Synthesis of Compounds

Magnesium strips (67.5g, 2812mmol) and diethyl ether (500 mL) were placed in a dry round bottom flask under nitrogen and iodine (500 mg) was added. Then, slowly dripping the solution of 2-bromo-3 '-chloro-1, 1' -biphenyl (240g, 900mmol) dissolved in diethyl ether (1000 mL) into the flask, heating to 35 ℃ after finishing dripping, and stirring for 3 hours; cooling the reaction liquid to 0 ℃, slowly dripping a diethyl ether (1000 mL) solution dissolved with adamantanone (112.5 g,745 mmol), heating to 35 ℃ after dripping, and stirring for 6 hours; cooling the reaction solution to room temperature, adding 5% hydrochloric acid to the reaction solution until the pH value is less than 7, stirring the solution for 1 hour, adding diethyl ether (1000 mL) to the reaction solution for extraction, combining organic phases, drying the combined organic phases by using anhydrous magnesium sulfate, filtering the combined organic phases, and removing the solvent under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as a mobile phase to obtain-Q-1 (210 g, yield 84%) as a solid intermediate.

Adding the intermediate-Q-1 (210g, 619.5 mmol), trifluoroacetic acid (211.5 g,1855 mmol) and dichloromethane (MC, 2500 mL) into a round-bottom flask, and stirring under nitrogen for 2 hours; then, an aqueous sodium hydroxide solution was added to the reaction solution to pH =8, liquid separation was performed, the organic phase was dried with anhydrous magnesium sulfate, filtration was performed, and the solvent was removed under reduced pressure; the crude product was subjected to silica gel column chromatography using dichloromethane/n-heptane (1).

2-bromo-1-chloro-3-iodobenzene (CAS. NO.: 1369793-66-7) (200g, 630.2mmol), phenylboronic acid (76.8g, 630.2mmol), tetrakis (triphenylphosphine) palladium (36.4g, 31.5 mmol), potassium carbonate (260.9g, 1890mmol), tetrabutylammonium chloride (8.72g, 31.5 mmol), 1.6L of toluene, 0.8L of ethanol and 0.4L of deionized water were charged into a three-necked flask, and the temperature was raised to 78 ℃ under the protection of nitrogen, followed by stirring for 6 hours; cooling the reaction liquid to room temperature, adding 500mL of toluene for extraction, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering to obtain filtrate, and concentrating the filtrate under reduced pressure to obtain a crude product; the obtained crude product was purified by silica gel column chromatography using n-heptane as a mobile phase, followed by recrystallization purification using a dichloromethane/n-heptane system (1.

Referring to the synthesis method of intermediate-a, intermediate-X shown in table 1 was synthesized except that SM-a-G was used instead of 2' -bromo-3-chlorobiphenyl. X may be B, C and D, and G may be 1,2 and 3.

TABLE 1

intermediate-D (30g, 93.4 mmol), pinacoldiboron diboronate (23.7g, 93.4mmol), tris (dibenzylideneacetone) dipalladium (0.9g, 0.9mmol), 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (0.8g, 1.8mmol), potassium acetate (18.3g, 186.9mmol) and 1, 4-dioxane (300 mL) were charged into a reaction flask, heated to 110 ℃ under nitrogen protection, and stirred under reflux for 5h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane (1).

In one embodiment, intermediate-X-M shown in Table 2 is synthesized with reference to the synthesis of intermediate-D-M, except that intermediate-X is used instead of intermediate-D for the preparation of intermediate-D-M, and the resulting intermediate-X-M is shown in Table 2 below.

TABLE 2

Adding intermediate-D-M (20g, 48.5mmol), p-bromoiodobenzene (13.7g, 48.5mmol), tetrakis (triphenylphosphine) palladium (2.8g, 2.4mmol), potassium carbonate (13.4g, 96.9mmol), tetrabutylammonium bromide (0.3g, 0.9mmol), toluene (160 mL), ethanol (80 mL) and deionized water (40 mL) into a round-bottomed flask, heating to 80 ℃ under the protection of nitrogen, and stirring for 12 hours; cooling the reaction solution to room temperature, adding toluene (100 mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the obtained crude product was purified by silica gel column chromatography using n-heptane as a mobile phase and then by recrystallization using a dichloromethane/ethyl acetate system (1.

In one embodiment, intermediate-S-X shown in Table 3 is synthesized with reference to the synthesis of intermediate-S-1, except that compound SMS-X is used instead of p-bromoiodobenzene for the preparation of intermediate-S-1, intermediate-X-M is used instead of intermediate-D-M for the preparation of intermediate-S-1, and each compound SMS-X and intermediate-X-M combination produces the only corresponding intermediate-S-X, as shown in Table 3 below:

TABLE 3

The intermediate-D (15g, 46.7mmol), SM-Z-1 (4.35g, 46.7mmol), tris (dibenzylideneacetone) dipalladium (0.8g, 0.93mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (0.20, 0.5mmol), sodium tert-butoxide (6.7g, 70.1mmol) and a toluene solvent (150 mL) were charged into a reaction flask, and the mixture was heated to 110 ℃ under nitrogen protection, and stirred under reflux for 3 hours. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system (1.

In one embodiment, intermediate-Z-X shown in Table 4 is synthesized with reference to the synthesis of intermediate-Z-1, except that compound SM-Z-X is used instead of SM-Z-1 for the preparation of intermediate-Z-1, intermediate-X is used instead of intermediate-D for the preparation of intermediate-Z-1, and each compound SM-Z-X and intermediate-X combination produces the unique corresponding intermediate-Z-X as shown in Table 4 below.

TABLE 4

Adding 3, 6-dibromofluorenone (100g, 295.8mmol), 1-naphthalene benzene boric acid (101.7g, 591.7mmol), tetrakis (triphenylphosphine) palladium (34.2g, 29.6 mmol), potassium carbonate (244.9g, 1775.1mmol), tetrabutylammonium chloride (8.2g, 29.6 mmol), toluene (800 mL), ethanol (400 mL) and deionized water (200 mL) into a three-neck flask, heating to 78 ℃ under the protection of nitrogen, and stirring for 8 hours; cooling the reaction liquid to room temperature, adding toluene (500 mL) for extraction, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering to obtain filtrate, and concentrating the filtrate under reduced pressure to obtain a crude product; the obtained crude product was purified by silica gel column chromatography using n-heptane as a mobile phase, followed by recrystallization purification using a dichloromethane/ethyl acetate (1.

In one embodiment, intermediate-C-X shown in Table 5 is synthesized with reference to the synthesis method of intermediate-A-1, except that compound SM-C-X is used instead of 3, 6-dibromofluorenone for preparing intermediate-A-1, and SM-C-Y is used instead of 1-naphthylphenylboronic acid for preparing intermediate-A-1, and each of the compounds SM-C-X and SM-C-Y can be combined to prepare intermediate-C-X uniquely corresponding thereto, and the prepared intermediate-C-X is shown in Table 5 below.

TABLE 5

The above-mentioned compound (1346010-03-4) (100g, 263.1mmol) was completely dissolved in tetrahydrofuran (1000 mL), then n-BuLi (18.5g, 289.4 mmol) was slowly added dropwise thereto at a temperature of-78 deg.C, and the mixture was stirred for 1 hour while maintaining the temperature. At the same temperature, methyl iodide (56.0 g,394.5 mmol) was added dropwise thereto, and then the temperature was slowly raised to room temperature, and then, after mixing for 15 hours, the reaction was stopped with a saturated aqueous ammonium chloride solution. The organic layer collected by extraction reaction using ethyl acetate was dried by using anhydrous magnesium sulfate three times, and distilled under reduced pressure, and the product was purified by silica gel column chromatography, thereby obtaining intermediate-B-4 (39.5g, 60%).

In one embodiment, intermediate-M-X shown in table 6 is synthesized with reference to the synthesis method of intermediate-B-4, except that compound SM-M-X is used instead of compound for preparing intermediate-B-4 (1346010-03-4) and SMY is used instead of methyl iodide for preparing intermediate-B-4. And each compound SM-M-X and SMY can be combined to prepare an intermediate-M-X which is uniquely corresponding to the compound SM-M-X, and the prepared intermediate-M-X is shown in the following table 6.

TABLE 6

Adding SM-1 (10.0g, 37.4mmol) and tetrahydrofuran (100 mL) into a three-neck reaction bottle at one time under the protection of nitrogen, starting stirring, uniformly stirring, cooling the system to-78 ℃, starting dropwise adding n-butyllithium (2.9g, 44.9mmol) after the temperature is stabilized, preserving heat for 1h at-78 ℃ after dropwise adding is finished, then diluting the intermediate-A-1 (17.7g, 41.1mmol) with tetrahydrofuran (40 mL), dropwise adding into the system, preserving heat for 1h at-78 ℃ after dropwise adding is finished, naturally heating to 25 ℃, and stirring for 12h. After completion of the reaction, the reaction solution was poured into water (200 mL), stirred for 10min, and then dichloromethane (200 mL) was added to conduct extraction operation 2 times, the organic phases were combined, dried over anhydrous magnesium sulfate and passed through a silica gel funnel, and then the filtrate was concentrated to dryness to give intermediate-D-A-1 (13.9 g, yield: 60%).

To a single-necked flask, intermediate-D-a-1 (10.0 g, 16.1mmol), trifluoroacetic acid (500 mL) were added, stirring was turned on, then gradually warmed to 80 ℃ and refluxed for 11h, after completion of the reaction, the reaction solution was poured into water (1: n-heptane =1:2 to give intermediate-E-A-1 (7.8 g, yield 80%).

In one embodiment, intermediate-D-M-X and intermediate-E-M-X shown in Table 7 are synthesized with reference to the synthesis of intermediate-D-A-1 except that intermediate-M-X is used in place of intermediate-A-1 for preparing intermediate-D-A-1 and SM-X is used in place of SM-1 for preparing intermediate-D-A-1, and each of the compound intermediates-M-X and SM-X in combination can prepare intermediate-D-M-X and intermediate-E-M-X corresponding thereto, and the prepared intermediates-D-M-X and intermediate-E-M-X are shown in tables 7 and 8 below.

TABLE 7

TABLE 8

A100 mL reaction flask was charged with intermediate-E-A-9 (2.0g, 5.1mmol), intermediate-Z-13 (2.3g, 5.1mmol), tris (dibenzylideneacetone) dipalladium (0.04g, 0.05mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.04g, 0.1mmol), sodium tert-butoxide (0.73g, 7.6mmol), and a toluene solvent (20 mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 hours. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound a-1 (2.9 g, yield: 75%). The mass spectrum is as follows: m/z =768.4 (M + H) ⁺ 。

In one embodiment, compounds M-X shown in Table 9 are synthesized with reference to the synthesis of compound-A-1, except that intermediate-E-M-X is used in place of intermediate-E-A-9 in the preparation of compound-A-1, intermediate-Z-X is used in place of intermediate-Z-13 in the preparation of compound-A-1, and each compound intermediate-E-M-X and intermediate-Z-X combination produces the only corresponding compound M-X, as shown in Table 9 below.

TABLE 9

The nuclear magnetic data of some of the compounds are shown in Table 10 below

Watch 10

HOMO energy level testing

The HOMO level and LUMO level and hole mobility of some of the compounds were determined using cyclic voltammetry. The test results are shown in tables 11-1 and 11-2.

Table 11-1: HOMO level, LUMO level and hole mobility of some compounds

Wherein the unit of hole mobility is cm ² /v·s。

HOMO and LUMO energy levels of some compounds in Table 11-2

As is apparent from tables 11-1 and 11-2, the difference in LUMO levels between the compounds of class D (e.g., compound D-1, compound D-2, compound D-4, compound D-5, compound D-7, compound D-8, compound D-12, compound D-14, compound D-15, compound D-17, compound D-18, etc.) and the electron blocking layer material EB-1 is less than 0.27eV, so that a smaller difference in LUMO levels results in electrons easily passing over the electron blocking layer into the hole transporting layer, resulting in a lower device lifetime. The LUMO energy levels of part of the A-type compounds (such as the compound A-1, the compound A-2, the compound A-4, the compound A-6, the compound A-7, the compound A-10 and the like) and the B-type compounds (such as the compound B-3, the compound B-8, the compound B-10, the compound B-18, the compound B-27 and the like) are higher than the LUMO energy level of EB-1 and are higher than the LUMO energy level of EB-1 by more than 0.26eV, so that electrons in the electron blocking layer are difficult to overcome the energy level barrier and are efficiently injected into the hole transport layer, the impact of the electrons on the hole transport layer is reduced, and the service life of the organic electronic light-emitting device can be prolonged.

As is apparent from tables 11-1 and 11-2, the LUMO level of the E-based compounds (e.g., compound E-2, compound E-5, compound E-6, compound E-7, compound E-8, compound E-9, compound E-11, compound E-12, compound E-14, compound E-15, compound E-17, compound E-18, compound E-19, etc.) is greatly different from the LUMO level of the electron barrier material EB-1 by more than 0.44eV. This makes it possible to efficiently block electrons from crossing the electron-blocking layer and entering hole transport when EB-1 is combined with an E-based compound as the electron-blocking layer. Furthermore, compounds of class E have a greater electron transport capacity than compounds of class D, and therefore have a higher hole mobility (e.g., a hole mobility greater than 6.0 × E) when compared to compounds of class D ^-5 cm ² V · s), for example, when the hole transport layer material is combined with a part of a group compounds (for example, compound a-48, compound a-49, compound a-50, compound a-51, compound a-52, compound a-53, and the like), and C group compounds (for example, compound C-1, compound C-2, compound C-4, compound C-9, compound C-12, compound C-20, compound C-21), electrons and holes can be more effectively recombined in the organic light emitting layer, and thus, the carrier utilization efficiency can be improved, and the light emitting efficiency of the device can be improved.

Preparation and performance evaluation of organic electroluminescent device

Example 1: fabrication of blue organic electroluminescent device

The anode was prepared by the following procedure: the thickness of the glass substrate deposited with the ITO/Ag/ITO three-layer material by magnetron sputtering is respectively

Cutting into 40mm (length) × 40mm (width) × 0.7mm (thickness), performing photolithography to prepare experimental substrate with cathode, anode and insulating layer patterns, and using ultraviolet ozone and O ₂ :N ₂ Plasma is used for surface treatment to increase the work function of the anode, and an organic solvent can be used for cleaning the surface of the ITO substrate to remove impurities and oil stains on the surface of the ITO substrate.

On the anode of the experimental substrate, compound a-1 was used as a host and compound PD was used as a guest, and the deposition rate ratio was 100

A Hole Injection Layer (HIL); vacuum evaporating Compound A-1 on the Hole Injection Layer (HIL) to a thickness of

A Hole Transport Layer (HTL).

The compound EB-1 was vapor deposited on the Hole Transport Layer (HTL) to a thickness of

Electron Blocking Layer (EBL).

The compound D-1 is used as a host material of a luminescent layer, the compound BD-1 is used as a guest material of the luminescent layer, and the compound D-1 and the guest material are simultaneously evaporated according to the evaporation rate ratio of 100

The organic light emitting layer (EML).

The compounds ET-1 and LiQ were mixed at a weight ratio of 1

A thick Electron Transport Layer (ETL).

Metal Yb is vapor-deposited on the electron transport layer 34 to have a thickness of

The Electron Injection Layer (EIL).

Then, magnesium (Mg) and silver (Ag) were mixed at a deposition rate of 1

The cathode of (1).

The thickness of the vapor deposition on the cathode is

Forming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device.

In example 1, the material structure used is as follows:

examples 2 to 24

In example 2, compound A-2 was used in place of compound A-1 in example 1, and compound D-2 was used in place of compound D-1 in example 1.

In example 3, compound A-4 was used in place of compound A-1 in example 1, and compound D-4 was used in place of compound D-1 in example 1.

In example 4, compound A-6 was used in place of compound A-1 in example 1, and compound D-5 was used in place of compound D-1 in example 1.

In example 5, compound A-7 was used in place of compound A-1 in example 1, and compound D-7 was used in place of compound D-1 in example 1.

In example 6, compound A-10 was used in place of compound A-1 in example 1, and compound D-8 was used in place of compound D-1 in example 1.

In example 7, compound A-48 was used in place of compound A-1 in example 1, and compound E-2 was used in place of compound D-1 in example 1.

In example 8, compound A-49 was used in place of compound A-1 in example 1, and compound E-5 was used in place of compound D-1 in example 1.

In example 9, compound A-50 was used in place of compound A-1 in example 1, and compound E-6 was used in place of compound D-1 in example 1.

In example 10, compound A-51 was used in place of compound A-1 in example 1, and compound E-7 was used in place of compound D-1 in example 1.

In example 11, compound A-52 was used in place of compound A-1 in example 1, and compound E-8 was used in place of compound D-1 in example 1.

In example 12, compound A-53 was used in place of compound A-1 in example 1, and compound E-9 was used in place of compound D-1 in example 1.

In example 13, compound B-3 was used in place of compound A-1 in example 1, and compound D-12 was used in place of compound D-1 in example 1.

In example 14, compound B-8 was used in place of compound A-1 in example 1, and compound D-14 was used in place of compound D-1 in example 1.

In example 15, compound B-10 was used in place of compound A-1 in example 1, and compound D-15 was used in place of compound D-1 in example 1.

In example 16, compound B-18 was used in place of compound A-1 in example 1, and compound D-17 was used in place of compound D-1 in example 1.

In example 17, compound B-27 was used in place of compound A-1 in example 1, and compound D-18 was used in place of compound D-1 in example 1.

In example 18, compound C-1 was used in place of compound A-1 in example 1, and compound E-11 was used in place of compound D-1 in example 1.

In example 19, compound C-2 was used in place of compound A-1 in example 1, and compound E-12 was used in place of compound D-1 in example 1.

In example 20, compound C-4 was used in place of compound A-1 in example 1, and compound E-14 was used in place of compound D-1 in example 1.

In example 21, compound C-9 was used in place of compound A-1 in example 1, and compound E-15 was used in place of compound D-1 in example 1.

In example 22, compound C-12 was used in place of compound A-1 in example 1, and compound E-17 was used in place of compound D-1 in example 1.

In example 23, compound C-20 was used in place of compound A-1 in example 1, and compound E-18 was used in place of compound D-1 in example 1.

In example 24, compound C-21 was used in place of compound A-1 in example 1, and compound E-19 was used in place of compound D-1 in example 1.

Comparative examples 1 to 3

An organic electroluminescent device was formed by the method shown in example 1 using the materials shown in Table 12. Wherein, the first and the second end of the pipe are connected with each other,

in comparative example 1, compound HT-1 was used in place of compound A-1 in example 1, and compound α, β -ADN was used in place of compound D-1 in example 1.

In comparative example 2, compound HT-2 was used in place of compound A-1 of example 1.

In comparative example 3, compound HT-3 was used in place of compound A-1 in example 1, and compound E-2 was used in place of compound D-1 in example 1.

Performance tests were performed on each of the organic electroluminescent devices prepared in examples 1 to 24 and comparative examples 1 to 3. Wherein the driving voltage, current efficiency, power efficiency, color coordinate, external Quantum Efficiency (EQE), etc. are 10mA/cm ² Measured at a current density of (2), T95 lifetime is actually 20mA/cm ² Is tested at a current density of (1). Through testing, the color coordinate CIE-x of each device is 0.140; the color coordinates CIE-y of each device were 0.050.

The performance test results of the respective organic electroluminescent devices are shown in table 12.

Table 12 materials and performance test results 2 of organic electroluminescent device

As can be seen from table 12, the driving voltages of the organic electroluminescent devices prepared in examples 1 to 24 all showed a certain reduction compared to the organic electroluminescent devices prepared in comparative examples 1 to 3, because the compound represented by chemical formula 1 of the present disclosure not only has a large conjugated system and a relatively rigid spiro system, but also the compound represented by chemical formula 1 has a relatively high hole transporting ability. As a direct proof, referring to the hole mobilities of the compounds of partial chemical formula 1 shown in Table 11-1, it can be seen that the hole mobilities of these compounds are all greater than 1.20E ^-5 cm ² /v·s。

Referring to table 12, the organic electroluminescent devices prepared in examples 1 to 6 and examples 13 to 17 had better lifetimes, increasing the T95 lifetime from 113 hours maximum to 153 hours to 167 hours, with an increase of at least 35%, compared to comparative examples 1 to 3. According to these examples, it was found that when a group a compound having a shallow LUMO level (e.g., a compound represented by formula a having a LUMO level shallower than 1.90 eV) or a group B compound (a compound represented by formula B) is used as a hole transport layer and a group D compound (a compound represented by formula D) is used as a host material of an organic light emitting layer, an organic electroluminescent device can significantly improve the lifetime of the organic electroluminescent device while maintaining a driving voltage and luminous efficiency without a significant drop or substantially constant, achieving an effect of improving the performance of the organic electroluminescent device. Referring to table 11-1, when the a-type compound or the B-type compound (compound represented by formula B) having a shallow LUMO energy level has a shallow LUMO energy level, it can efficiently block electrons from entering the hole transport layer, prevent the hole transport material from failing due to accelerated aging under the impact of electron current, and to some extent, make up for the defect that the electron blocking layer material in these embodiments cannot efficiently block electrons.

Referring to table 12, the organic electroluminescent devices prepared in examples 7 to 12 and 18 to 24 had higher luminous efficiencies than those of comparative examples 1 to 3, and the current efficiencies were increased from 6.01cd/a to 6.28cd/a to 7.03cd/a to 7.19cd/a, which were at least 12%. These examples show that when having a low LUMO level and high mobility (hole mobility greater than 6.0 × e) ^-5 cm ² V · s) or a C-type compound (a compound represented by chemical formula C) as a hole transport layer, and an E-type compound (a compound represented by chemical formula E) as a host material of the organic light emitting layer, the E-type compound has a stronger electron transport ability, so that when the E-type compound is combined with a hole transport layer material having a high hole mobility, electrons and holes can be more effectively recombined in the organic light emitting layer, thereby improving the carrier utilization efficiency and the light emitting efficiency of the device.

The organic electroluminescent device can improve the luminous efficiency without obvious reduction in the aspects of driving voltage, device service life and the like, thereby achieving the effect of improving the performance of the organic electroluminescent device. It is understood that although the organic electroluminescent device of the embodiments has an improved luminous efficiency, the aging speed of each film layer of the organic electroluminescent device may be accelerated, and there is a risk of reducing the device lifetime of the organic electroluminescent device.

However, the E-type compound and the electron blocking layer material have large LUMO energy level difference, electrons can be efficiently blocked from entering the electron blocking layer, and further impact of electron current on the hole transport layer is avoided, so that the service life of the organic electroluminescent device can be greatly prolonged; under the condition that the two factors are mutually offset, the organic electroluminescent devices in the embodiments can obtain the improvement of the luminous efficiency on the premise of not sacrificing the service life of the devices.

Examples 25 to 33

In example 25, compound a-2 was used instead of compound a-1 in example 1, compound EB-2 was used instead of compound EB-1 in example 1, and compound D-4 was used instead of compound D-1 in example 1, respectively.

In example 26, compound a-4 was used instead of compound a-1 in example 1, compound EB-17 was used instead of compound EB-1 in example 1, and compound D-5 was used instead of compound D-1 in example 1, respectively.

In example 27, compound a-6 was used instead of compound a-1 in example 1, compound EB-18 was used instead of compound EB-1 in example 1, and compound D-7 was used instead of compound D-1 in example 1, respectively.

In example 28, compound a-7 was used instead of compound a-1 in example 1, compound EB-3 was used instead of compound EB-1 in example 1, and compound D-14 was used instead of compound D-1 in example 1, respectively.

In example 29, compound a-10 was used instead of compound a-1 in example 1, compound EB-4 was used instead of compound EB-1 in example 1, and compound E-2 was used instead of compound D-1 in example 1, respectively.

In example 30, compound a-48 was used instead of compound a-1 in example 1, compound EB-6 was used instead of compound EB-1 in example 1, and compound E-5 was used instead of compound D-1 in example 1, respectively.

In example 31, compound a-49 was used instead of compound a-1 in example 1, EB-7 was used instead of compound EB-1 in example 1, and compound E-6 was used instead of compound D-1 in example 1, respectively.

In example 32, compound a-50 was used in place of compound a-1 in example 1, compound EB-15 was used in place of compound EB-1 in example 1, and compound E-7 was used in place of compound D-1 in example 1, respectively.

In example 33, compound a-51 was used instead of compound a-1 in example 1, compound EB-16 was used instead of compound EB-1 in example 1, and compound E-18 was used instead of compound D-1 in example 1, respectively.

Comparative example 4

In comparative example 4, compound HT-1 was used in place of compound A-1 of example 1.

Performance tests were performed on each of the organic electroluminescent devices prepared in examples 25 to 33 and comparative example 4. Wherein the driving voltage, current efficiency, power efficiency, color coordinate, external Quantum Efficiency (EQE), etc. are 10mA/cm ² Measured at a current density of (1), T95 lifetime is actually 20mA/cm ² Is tested at a current density of (1). Through testing, the color coordinate CIE-x of each device is 0.140; the color coordinates CIE-y of each device were 0.050.

The results of performance testing of the respective organic electroluminescent devices are shown in table 13.

Table 13 materials and performance test results of organic electroluminescent device

As can be seen from table 13, the organic electroluminescent devices prepared in examples 1 and 25 to 33 had a small reduction in driving voltage and a large increase in lifetime, as compared to the organic electroluminescent devices prepared in comparative examples 4 and 5, which was associated with the use of the high mobility compound a as a hole transport material. And the energy levels of the hole transport layer material, the electron blocking layer and the main body material are matched, so that good carrier balance is achieved, the influence of enriched electrons on the service life is reduced, and the service life of the organic electroluminescent device is finally prolonged.

In the embodiments of the present disclosure, the compound of formula 1 is used as a hole transport layer of an organic electroluminescent device, and the compound of formula 4 is used as a host material of an organic light emitting layer of the organic electroluminescent device, so that at least one aspect of the light emitting efficiency and the device lifetime of the organic electroluminescent device can be improved, and the driving voltage, the light emitting efficiency and the device lifetime of the organic electroluminescent device are not sacrificed, which improves the performance of the organic electroluminescent device.

Claims

1. An organic electroluminescent device is characterized by comprising an anode, a hole transport layer, an organic light emitting layer, an electron transport layer and a cathode which are sequentially stacked, wherein the hole transport layer comprises a compound shown in chemical formula 1, and the organic light emitting layer comprises a compound shown in chemical formula 4;

represents a chemical bond;

a is a group represented by chemical formula 2;

Ar ₂ is a group represented by chemical formula 3;

Ar ₄ selected from the group consisting of hydrogen, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;

the L, L', ar ₁ 、Ar ₃ And Ar ₄ The substituents on the above groups are each independently selected from deuterium, a halogen group, a cyano group, a heteroaryl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, and a phosphonooxy group having 6 to 18 carbon atoms.

2. The organic electroluminescent device according to claim 1, wherein the compound of formula 1 is selected from the group consisting of the following formulae:

3. the organic electroluminescent device according to claim 1 or 2, wherein R is ₁ And R ₂ The same or different, and each is independently selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

4. The organic electroluminescent device according to claim 1 or 2, wherein R is ₁ And R ₂ Identical or different and are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl.

5. The organic electroluminescent device according to claim 1 or 2, wherein R is ₁ And R ₂ Are respectively selected from isopropyl and tert-butyl.

6. The organic electroluminescent device according to claim 1 or 2, wherein L is selected from a single bond, and a substituted or unsubstituted arylene group having 6 to 18 carbon atoms.

7. The organic electroluminescent device according to claim 1 or 2, wherein L is selected from a single bond or a group of formula j-1 to formula j-6:

wherein M is ₂ Selected from a single bond or

E ₁ ～E ₁₀ Each independently selected from: deuterium, a halogen group, a cyano group, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 1 to 10 carbon atoms, an aryloxy group having a halogen atomIs arylthio of 6 to 18, phosphorus oxygen of 6 to 18 carbon atoms, heteroaryl of 3 to 18 carbon atoms or aryl of 6 to 18 carbon atoms;

e ₁ is a substituent E ₁ The number of (e) ₁ Selected from 0, 1,2,3 or 4; when e is ₁ When greater than 1, any two of E ₁ The same or different;

e ₂ is a substituent E ₂ The number of (e) ₂ Selected from 0, 1,2,3 or 4; when e is ₂ When greater than 1, any two of E ₂ The same or different;

e ₃ is a substituent E ₃ The number of (e) ₃ Selected from 0, 1,2,3 or 4; when e is ₃ When greater than 1, any two of E ₃ The same or different;

e ₄ is a substituent E ₄ The number of (e) ₄ Selected from 0, 1,2,3 or 4; when e is ₄ When greater than 1, any two of E ₄ The same or different;

e ₅ is a substituent E ₅ The number of (e) ₅ Selected from 0, 1,2,3 or 4; when e is ₅ When greater than 1, any two of E ₅ The same or different;

e ₆ is a substituent E ₆ Number of (e) ₆ Selected from 0, 1,2,3 or 4; when e is ₆ When greater than 1, any two of E ₆ The same or different;

e ₇ is a substituent E ₇ The number of (e) ₇ Selected from 0, 1,2,3,4, 5 or 6; when e is ₇ When greater than 1, any two of E ₇ The same or different;

e ₈ is a substituent E ₈ The number of (e) ₈ Selected from 0, 1,2,3,4, 5,6,7 or 8; when e is ₈ When greater than 1, any two of E ₈ The same or different;

e ₉ is a substituent E ₉ Number of (e) ₉ Selected from 0, 1,2,3,4, 5,6,7 or 8; when e is ₉ When greater than 1, any two of E ₉ The same or different;

e ₁₀ is a substituent E ₁₀ The number of (e) ₁₀ Selected from 0, 1,2,3 or 4; when e is ₁₀ When greater than 1, any two of E ₁₀ The same or different.

8. The organic electroluminescent device according to claim 1 or 2, wherein L is selected from a single bond or a group consisting of:

9. the organic electroluminescent device according to claim 1 or 2, characterized in that Ar is Ar ₁ 、Ar ₃ Each independently selected from substituted or unsubstituted aryl groups having 6 to 20 carbon atoms;

Ar ₄ selected from hydrogen or substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.

10. The organic electroluminescent device according to claim 1 or 2, wherein Ar is Ar ₁ 、Ar ₃ Each independently selected from the group consisting of substituents represented by formula i-1 to formula i-11;

Ar ₄ selected from hydrogen or a substituent represented by the formula i-1 to the formula i-11:

wherein M is ₁ Selected from a single bond or

H ₁ ～H ₂₁ Each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, alkoxy having 1 to 10 carbon atoms, alkylamino having 1 to 10 carbon atoms, alkylthio having 1 to 10 carbon atoms, and trioxane having 3 to 12 carbon atomsA silyl group, an arylsilyl group having 8 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms; h ₄ ～H ₂₀ Any of which may be independently selected from aryl groups having 6 to 20 carbon atoms;

h ₁ is a substituent H ₁ Number of (a), h ₁ Selected from 1,2,3,4 or 5; when h is ₁ When greater than 1, any two H ₁ The same or different; optionally, any two adjacent H ₁ Are connected with each other to form a ring;

h ₂ is a substituent group H ₂ Number of (a), h ₂ Selected from 1,2,3 or 4; when h is generated ₂ When greater than 1, any two H ₂ The same or different; optionally, any two adjacent H ₂ Are connected with each other to form a ring;

h ₃ is a substituent H ₃ Number of (b), h ₃ Selected from 1,2,3,4 or 5; when h is generated ₃ When greater than 1, any two H ₃ The same or different; optionally, any two adjacent H ₃ Are connected with each other to form a ring;

h ₄ is a substituent H ₄ Number of (a), h ₄ Selected from 1,2,3,4 or 5; when h is generated ₄ When greater than 1, any two H ₄ The same or different; optionally, any two adjacent H ₄ Are connected with each other to form a ring;

h ₅ is a substituent H ₅ Number of (b), h ₅ Selected from 1,2 or 3; when h is generated ₅ When greater than 1, any two H ₅ The same or different; optionally, any two adjacent H ₅ Are connected with each other to form a ring;

h ₆ is a substituent H ₆ Number of (a), h ₆ Selected from 1,2,3,4 or 5; when h is ₆ When greater than 1, any two H ₆ The same or different; optionally, any two adjacent H ₆ Are connected with each other to form a ring;

h ₇ is a substituent group H ₇ Number of (a), h ₇ Selected from 1,2,3 or 4; when h is generated ₇ Greater than 1 hourAny two of H ₇ The same or different; optionally, any two adjacent H ₇ Are connected with each other to form a ring;

h ₈ is a substituent H ₈ Number of (a), h ₈ Selected from 1,2,3 or 4; when h is generated ₈ When greater than 1, any two H ₈ The same or different; optionally, any two adjacent H ₈ Are connected with each other to form a ring;

h ₉ is a substituent group H ₉ Number of (b), h ₉ Selected from 1,2,3,4 or 5; when h is generated ₉ When greater than 1, any two H ₉ The same or different; optionally, any two adjacent H ₉ Are connected with each other to form a ring;

h ₁₀ is a substituent group H ₁₀ Number of (a), h ₁₀ Selected from 1,2,3,4, 5,6 or 7; when h is ₁₀ When greater than 1, any two H ₁₀ The same or different; optionally, any two adjacent H ₁₀ Are connected with each other to form a ring;

h ₁₁ is a substituent group H ₁₁ Number of (b), h ₁₁ Selected from 1,2,3,4, 5,6,7,8 or 9; when h is ₁₁ When greater than 1, any two H ₁₁ The same or different; optionally, any two adjacent H ₁₁ Are connected with each other to form a ring;

h ₁₂ is a substituent H ₁₂ Number of (a), h ₁₂ Selected from 1,2,3 or 4; when h is generated ₁₂ When greater than 1, any two H ₁₂ The same or different; optionally, any two adjacent H ₁₂ Are connected with each other to form a ring;

h ₁₃ is a substituent group H ₁₃ Number of (a), h ₁₃ Selected from 1,2,3,4, 5 or 6; when h is ₁₃ When greater than 1, any two H ₁₃ The same or different; optionally, any two adjacent H ₁₃ Are connected with each other to form a ring;

h ₁₄ is a substituent H ₁₄ Number of (b), h ₁₄ Selected from 1,2,3,4 or 5; when h is ₁₄ When greater than 1, any two H ₁₄ The same or different; optionally, any two adjacentH ₁₄ Are connected with each other to form a ring;

h ₁₅ is a substituent H ₁₅ Number of (b), h ₁₅ Selected from 1,2,3 or 4; when h is ₁₅ When greater than 1, any two H ₁₅ The same or different; optionally, any two adjacent H ₁₅ Are connected with each other to form a ring;

h ₁₆ is a substituent group H ₁₆ Number of (a), h ₁₆ Selected from 1,2,3 or 4; when h is generated ₁₆ When greater than 1, any two H ₁₆ The same or different; optionally, any two adjacent H ₁₆ Are connected with each other to form a ring;

h ₁₇ is a substituent H ₁₇ Number of (a), h ₁₇ Selected from 1,2 or 3; when h is generated ₁₇ When greater than 1, any two H ₁₇ The same or different; optionally, any two adjacent H ₁₇ Are connected with each other to form a ring;

h ₁₈ is a substituent H ₁₈ Number of (a), h ₁₈ Selected from 1,2,3 or 4; when h is generated ₁₈ When greater than 1, any two H ₁₈ The same or different; optionally, any two adjacent H ₁₈ Are connected with each other to form a ring;

h ₁₉ is a substituent H ₁₉ Number of (a), h ₁₉ Selected from 1,2,3,4, 5,6 or 7; when h is generated ₁₉ When greater than 1, any two H ₁₉ The same or different; optionally, any two adjacent H ₁₉ Are connected with each other to form a ring;

h ₂₀ is a substituent H ₂₀ Number of (a), h ₂₀ Selected from 1,2,3,4, 5,6,7 or 8; when h is generated ₂₀ When greater than 1, any two H ₂₀ The same or different; optionally, any two adjacent H ₂₀ Are connected with each other to form a ring;

h ₂₁ is a substituent group H ₂₁ Number of (b), h ₂₁ Selected from 1,2,3 or 4; when h is ₂₁ When greater than 1, any two H ₂₁ The same or different; optionally, any two adjacent H ₂₁ Are connected with each other to form a ring;

K ₁ is selected from O、S、Se、N(H ₂₂ )、C(H ₂₃ H ₂₄ )、Si(H ₂₃ H ₂₄ ) (ii) a Wherein H ₂₂ 、H ₂₃ 、H ₂₄ Each independently selected from: an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms;

11. The organic electroluminescent device according to claim 1 or 2, wherein Ar is Ar ₁ Selected from the group consisting of:

12. the organic electroluminescent device according to claim 1 or 2, wherein the compound represented by chemical formula 1 is selected from the group consisting of:

wherein when n is ₃ When =0, the structural formula of chemical formula 1 is

When n is ₃ =2, and R ₃ And R ₄ When hydrogen is simultaneously present, the structural formula of formula 1 is

"-" indicates that R is absent at the 1,2,3, 4-positions of chemical formula 1 ₁ Substituted, "- -" indicates that the 5,6,7, 8-position of chemical formula 1 has no R ₂ Substitution;

L-A, L-B, L-C, L-D, L-E, L-F, L-G, L-H, L-I, L-J, L-K represent L of different structures and respectively correspond to the groups shown in the following

Is shown and

is connected to, represents and

is

Connecting;

13. According to claim1 or 2, wherein Ar is ₃ Selected from the group consisting of:

14. the organic electroluminescent device according to claim 1 or 2, wherein Ar is Ar ₄ Selected from hydrogen, phenyl, naphthyl, phenanthryl, anthryl and pyrenyl.

15. The organic electroluminescent device according to claim 1 or 2, wherein L' is selected from the group consisting of groups represented by formula j-1 to formula j-10:

wherein, M ₂ Selected from a single bond or

e ₆ is a substituent E ₆ The number of (e) ₆ Selected from 0, 1,2,3 or 4; when e is ₆ When greater than 1, any two of E ₆ The same or different;

e ₉ is a substituent E ₉ The number of (e) ₉ Selected from 0, 1,2,3,4, 5,6,7 or 8; when e is ₉ When greater than 1, any two of E ₉ The same or different;

e ₁₀ is a substituent E ₁₀ The number of (e) ₁₀ Selected from 0, 1,2,3 or 4; when e is ₁₀ When greater than 1, any two of E ₁₀ The same or different;

e ₁₁ to substitute forRadical E ₁₁ Number of (e) ₁₁ Selected from 0, 1,2 or 3; when e is ₁₁ When greater than 1, any two of E ₁₁ The same or different;

e ₁₂ is a substituent E ₁₂ Number of (e) ₁₂ Selected from 0, 1,2 or 3; when e is ₁₂ When greater than 1, any two of E ₁₂ The same or different;

e ₁₃ is a substituent E ₁₃ The number of (e) ₁₃ Selected from 0, 1,2,3,4 or 5; when e is ₁₃ When greater than 1, any two of E ₁₃ The same or different;

e ₁₄ is a substituent E ₁₄ The number of (e) ₁₄ Selected from 0, 1,2,3,4 or 5; when e is ₁₄ When greater than 1, any two of E ₁₄ The same or different;

e ₁₅ is a substituent E ₁₅ The number of (e) ₁₅ Selected from 0, 1,2,3,4 or 5; when e is ₁₅ When greater than 1, any two of E ₁₅ The same or different;

16. The organic electroluminescent device according to claim 1 or 2, wherein L' is selected from the group consisting of:

17. the organic electroluminescent device according to claim 1 or 2, wherein the compound represented by chemical formula 4 is selected from the group consisting of:

18. the organic electroluminescent device according to claim 1 or 2, further comprising a hole injection layer provided between the anode and the hole transport layer; the hole injection layer includes a compound represented by chemical formula 1 and a compound represented by chemical formula 5;

19. The organic electroluminescent device according to claim 18, wherein the Ar is ₅ 、Ar ₆ 、Ar ₇ Are all completely substituted.

20. The organic electroluminescent device according to claim 1 or 2, further comprising an electron blocking layer disposed between the hole transport layer and the organic light emitting layer; the electron blocking layer includes a compound represented by chemical formula 6:

wherein R is ₁₀ And R ₁₁ Same or different, and are independently selected from deuterium, fluorine, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, a cyano group, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms;

L ₁ and L ₂ The same or different, each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms; and L is ₁ And L ₂ Not being a single bond at the same time;

n ₄ is R ₁₀ And is selected from 0, 1,2,3 or 4; when n is ₄ When not less than 2, any two R ₁₀ The same or different;

21. The organic electroluminescent device according to claim 20, wherein the compound represented by chemical formula 6 is selected from the group consisting of:

22. an electronic device comprising the organic electroluminescent element according to any one of claims 1 to 21.