CN118084974A

CN118084974A - OLED luminescent compound, organic electroluminescent element and application thereof

Info

Publication number: CN118084974A
Application number: CN202410150142.XA
Authority: CN
Inventors: 李祥智; 崔建新; 陈奇; 李泽鹏; 谢哲俨; 金光哲
Original assignee: Haining Yinuoweite Technology Co ltd
Current assignee: Haining Yinuoweite Technology Co ltd
Priority date: 2023-04-07
Filing date: 2024-02-02
Publication date: 2024-05-28
Also published as: WO2024207937A1

Abstract

The invention belongs to the technical field of photoelectric materials, and relates to an OLED luminescent compound, which has a structure shown in a formula (1),One of Ar ¹、Ar² of formula (1) is selected fromR ¹、R² is independently selected from R substituted or unsubstituted C6-C30 aryl, R substituted or unsubstituted C3-C30 heteroaryl; the other is selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl; l ¹、L² is independently selected from a bond, R is substituted or unsubstituted C6-C30 arylene, R is substituted or unsubstituted C3-C30 heteroarylene, and each R is independently selected from one or more of deuterium, halogen, cyano, silane, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

Description

OLED luminescent compound, organic electroluminescent element and application

Technical Field

The invention belongs to the technical field of photoelectric materials, and particularly relates to an OLED luminescent compound, an organic electroluminescent element and application.

Background

The organic/high molecular electroluminescent (OLED/PLED) refers to the phenomenon that an organic/high molecular material with semiconductor characteristics emits light under the excitation action of an electric field, has the advantages of low driving voltage, high luminous efficiency, high response speed, ultra-light and ultra-thin performance, capability of being manufactured on a flexible substrate and the like, and has very wide application prospects in two fields of flat panel display and solid illumination.

According to the working principle of the device, the main contents of the research of the organic electroluminescent material and the device comprise the following aspects: active layer materials (red, green, blue trichromatic luminescent materials, including fluorescent materials and phosphorescent materials), matching materials for device assembly (hole and electron injection and transport materials), interface materials (anode and cathode interface modification materials), electrode materials (ITO electrodes, metal electrodes), device structures (multilayer devices, stacked devices), driving techniques (polysilicon TFTs, metal oxide TFTs, organic TFTs, etc.), packaging techniques (glass-oriented substrates, flexible substrates, etc.). The luminous efficiency, the color purity and the service life are important indexes for evaluating the comprehensive performance of the organic electroluminescent material and the device, and the yield and the price are key elements for determining the scale industrialization of the organic electroluminescent device.

Over the last decade, OLEDs have evolved as a new display technology, and OLED devices have substantially reached practical requirements in terms of light emission brightness, light emission efficiency, and lifetime. However, for large-sized OLED display, there is also a need for greatly improving the performance of luminous efficiency, lifetime, and the like.

Therefore, development of novel materials is urgently required to improve the luminous efficiency and the lifetime of the device.

Disclosure of Invention

The object of the present invention is to provide an OLED light-emitting compound, and an organic electroluminescent element prepared using the same can realize reduced driving voltage and durable service life.

The technical scheme adopted for solving the technical problems is as follows:

an OLED light-emitting compound having a structure represented by formula (1),

One of Ar ¹、Ar² is selected fromR ¹、R² is independently selected from R substituted or unsubstituted C6-C30 aryl, R substituted or unsubstituted C3-C30 heteroaryl; the other is selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl;

l ¹、L² is each independently selected from the group consisting of a bond, R substituted or unsubstituted C6-C30 arylene, R substituted or unsubstituted C3-C30 heteroarylene,

Each R is independently selected from one or a combination of more of deuterium, halogen, cyano, silane, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl and C3-C30 heteroaryl.

Representing the substitution position.

In the OLED luminescent compound, the hetero atom in the heteroaryl and the heteroarylene is at least one selected from O, S, N, P and Si.

Preferably, ar ¹、Ar² is notThe radicals being selected fromOr

In formula (2), X ¹ is selected from a bond, CR ^X1、O、S、N、NR^X1',X² is selected from a bond, CR ^X2、O、S、N、NR^X2',X³ is selected from a bond, CR ^X3、O、S、N、NR^X3',X⁴ is selected from a bond, CR ^X4、O、S、N、NR^X4',X⁵ is selected from a bond, CR ^X5、O、S、N、NR^X5',X⁶ is selected from a bond, CR ^X6、O、S、N、NR^X6',

The number of the connecting bonds in X ¹-X⁶ is 0 or 1,O is 0 or 1, the number of S is 0 or 1, and the number of N is 0,1, 2 or 3; the number of NR ^X1' is 0 or 1, the number of NR ^X2' is 0 or 1, the number of NR ^X3' is 0 or 1, the number of NR ^X4' is 0 or 1, the number of NR ^X5' is 0 or 1, the number of NR ^X6' is 0 or 1, R ^X1-R^X6、R^X1'-R^X6' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C1-C10 alkyl, R substituted or unsubstituted C3-C10 cycloalkyl, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl;

(further explanation is that when X ¹ is selected from O, S or NR ^X1', X ¹ is connected with the adjacent X ² by a single bond, X ¹ is connected with the adjacent X ⁶ by a single bond or a double bond, when X ¹ is selected from a connecting bond, X ¹ is connected with X ⁶ by a single bond or a double bond, when X ² is selected from O, S or NR ^X2', X ² is connected with the adjacent X ¹ by a single bond, and X ² is connected with the adjacent X ³ by a single bond or a double bond, when X ² is selected from a connecting bond, X ¹ is connected with X ³ by a single bond or a double bond; when X ³ is selected from O, S or NR ^X3', the connection between X ³ and the adjacent X ² is single bond, the connection between X ³ and the adjacent X ⁴ is single bond, and when X ³ is selected from the connection bond, the connection between X ² and X ⁴ is single bond or double bond; when X ⁴ is selected from O, S or NR ^X4', the connection between X ⁴ and the adjacent X ³ is single bond, the connection between X ⁴ and the adjacent X ⁵ is single bond, and when X ⁴ is selected from the connection bond, the connection between X ³ and X ⁵ is single bond or double bond; when X ⁶ is selected from O, S or NR ^X6', the connection between X ⁶ and the adjacent X ¹ is single bond, the connection between X ⁶ and the adjacent X ⁵ is single bond, and when X ⁶ is selected from the connection bond, the connection between X ¹ and X ⁵ is single bond or double bond);

in formula (3), Y ¹ is selected from a bond, C (R ^Y1)_n1、O、S、N、NR^Y1',Y² is selected from a bond, C (R ^Y2)_n2、O、S、N、NR^Y2',Y³ is selected from a bond, C (R ^Y3)_n3、O、S、N、NR^Y3',Y⁴ is selected from a bond, C (R ^Y4)_n4、O、S、N、NR^Y4',Y⁵ is selected from a bond, C (R ^Y5)_n5、O、S、N、NR^Y5',Y⁶ is selected from a bond, C (R ^Y6)_n6、O、S、N、NR^Y6',Y⁷ is selected from a bond, C (R ^Y7)_n7、O、S、N、NR^Y7',Y⁸ is selected from a bond, C (R ^Y8)_n8、O、S、N、NR^Y8',

N1 is selected from 1 or 2, n2 is selected from 1 or 2, n3 is selected from 1 or 2, n4 is selected from 1 or 2, n5 is selected from 1 or 2, n6 is selected from 1 or 2, n7 is selected from 1 or 2, n8 is selected from 1 or 2,

The number of linkages in Y ¹-Y⁸ is 0 or 1,O is 0 or 1, the number of S is 0 or 1, the number of N is 0, 1, 2, 3, the number of NR ^Y1' is 0 or 1, the number of NR ^Y2' is 0 or 1, the number of NR ^Y3' is 0 or 1, the number of NR ^Y4' is 0 or 1, the number of NR ^Y5' is 0 or 1, the number of NR ^Y6' is 0 or 1, the number of NR ^Y7' is 0 or 1, the number of NR ^Y8' is 0 or 1, R ^Y1-R^Y8、R^Y1'-R^Y8' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C1-C10 alkyl, R substituted or unsubstituted C3-C10 cycloalkyl, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl,

Adjacent R ^Y1-R^Y8 are not linked, or at least one pair of R ^Y1 and R ^Y8、R^Y1 and R ^Y2、R^Y2 and R ^Y3、R^Y3 and R ^Y4、R^Y4 and R ^Y5、R^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 are linked to form a ring C. The ring C is selected from R substituted or unsubstituted C6-C60 aromatic ring, R substituted or unsubstituted C6-C30 unsaturated carbocycle, R substituted or unsubstituted C3-C30 heteroaromatic ring;

The carbon atom in formula (3) is marked K ¹、K², which is explained further,

When Y ¹ is selected from C (R ^Y1)₂, O, S or NR ^Y1', single bond connection is formed between Y ¹ and adjacent Y ², single bond connection is formed between Y ¹ and adjacent carbon corresponding to K ¹, when Y ¹ is selected from a connecting bond, single bond connection is formed between Y ² and carbon corresponding to K ¹, when Y ² is selected from C (R ^Y2)₂, O, S or NR ^Y2', single bond connection is formed between Y ² and adjacent Y ¹, single bond connection is formed between Y ² and adjacent Y ³, and when Y ² is selected from a connecting bond, single bond or double bond connection is formed between Y ² and Y ³; when Y ³ is selected from C (R ^Y3)₂, O, S or NR ^Y3', single bond connection is formed between Y ³ and adjacent Y ², single bond connection is formed between Y ³ and adjacent Y ⁴, when Y ³ is selected from a connecting bond, single bond or double bond connection is formed between Y ² and Y ⁴, when Y ⁴ is selected from C (R ^Y4)₂, O, S or NR ^Y4', single bond connection is formed between Y ⁴ and adjacent Y ³, single bond connection is formed between Y ⁴ and carbon corresponding to adjacent K ², and when Y ⁴ is selected from a connecting bond, single bond connection is formed between Y ⁴ and carbon corresponding to K ²; when Y ⁵ is selected from C (R ^Y5)₂, O, S or NR ^Y5', single bond connection is formed between Y ⁵ and adjacent Y ⁶, single bond connection is formed between Y ⁵ and adjacent carbon corresponding to K ², when Y ⁵ is selected from a connecting bond, single bond connection is formed between Y ⁵ and carbon corresponding to K ², when Y ⁶ is selected from C (R ^Y6)₂, O, S or NR ^Y6', single bond connection is formed between Y ⁶ and adjacent Y ⁵, single bond connection is formed between Y ⁶ and adjacent Y ⁷, and when Y ⁶ is selected from a connecting bond, single bond or double bond connection is formed between Y ⁵ and Y ⁷; when Y ⁷ is selected from C (R ^Y7)₂, O, S or NR ^Y7', single bond connection is formed between Y ⁷ and adjacent Y ⁶, single bond connection is formed between Y ⁷ and adjacent Y ⁸, when Y ⁷ is selected from a connecting bond, single bond or double bond connection is formed between Y ⁶ and Y ⁸, when Y ⁸ is selected from C (R ^Y8)₂, O, S or NR ^Y8', single bond connection is formed between Y ⁸ and adjacent Y ⁷, single bond connection is formed between Y ⁸ and carbon corresponding to adjacent K ¹, and when Y ⁸ is selected from a connecting bond, single bond connection is formed between Y ⁷ and carbon corresponding to K ¹.

Preferably, in formula (2) X ¹ is selected from CR ^X1、N,X² from CR ^X2、N,X³ from CR ^X3、N,X⁴ from CR ^X4、N,X⁵ from CR ^X5、N,X⁶ from CR ^X6, N, and the number of N in X ¹-X⁶ is 0, 1,2, 3.

Preferably, in formula (3) Y ¹ is selected from a bond, Y ⁴ is selected from C (R ^Y4)_n4、O、S、NR^Y4',Y² is selected from N, C (R ^Y2)_n2,Y³ is selected from N, C (R ^Y3)_n3,Y⁵ is selected from N, C (R ^Y5)_n5,Y⁶ is selected from N, C (R ^Y6)_n6,Y⁷ is selected from N, C (R ^Y8)_n8 and the number of N in Y ²-Y³、Y⁵-Y⁸ is 0 or1 or 2, R ^Y2-R^Y3、R^Y5-R^Y8 is not linked to form a ring, or at least one pair of R ^Y2 and R ^Y3、R^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 are linked to form a ring C.

More preferably, in formula (3) Y ¹ is selected from a bond, Y ⁴ is selected from C (R ^Y4)_n4、O、S,Y² is selected from C (R ^Y2)_n2,Y³ is selected from C (R ^Y3)_n3,Y⁵ is selected from C (R ^Y5)_n5,Y⁶ is selected from C (R ^Y6)_n6,Y⁷ is selected from C (R ^Y7)_n7,Y⁸ is selected from C (R ^Y8)_n8,n4＝2,n2＝1,n3＝1,n5＝1,n6＝1,n7＝1,n8＝1,R^Y2-R^Y3 is linked to form a ring C, R ^Y5-R^Y8 is not linked to form a ring).

More preferably, in formula (3) Y ¹ is selected from a bond, Y ⁴ is selected from NR ^Y4',Y² is selected from C (R ^Y2)_n2,Y³ is selected from C (R ^Y3)_n3,Y⁵ is selected from N or C (R ^Y5)_n5,Y⁶ is selected from C (R ^Y6)_n6,Y⁷ is selected from C (R ^Y7)_n7,Y⁸ is selected from C (R ^Y8)_n8,n2＝1,n3＝1,n5＝1,n6＝1,n7＝1,n8＝1,R^Y2-R^Y3 is linked to form a ring C, R ^Y5-R^Y8 is not linked to form a ring). Preferably, Y ¹ in formula (3) is selected from O, S, N, NR ^Y1',Y² to O, S, N, NR ^Y2'、C(R^Y2)_n2,Y³ to be a bond, Y ⁴ to O, S, N, NR ^Y4',Y⁵ to N, C (R ^Y5)_n5,Y⁶ to N, C (R ^Y6)_n6,Y⁷ to N, C (R ^Y7)_n7,Y⁸ to N, C (R ^Y8)_n8,Y¹-Y²、Y⁴-Y⁸ has N number of 0, 1, 2, O number of 0 or 1, S number of 0 or 1, R ^Y5-R^Y8 is not bonded to form a ring, or at least one pair of R ^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 are linked into a ring C. More preferably, the number of N in Y ¹-Y²、Y⁴-Y⁸ is 1. More preferably, the number of N in Y ¹-Y²、Y⁴-Y⁸ is 2. More preferably, Y ⁴ is selected from N.

Preferably, Y ¹ in formula (3) is selected from C (R ^Y1)_n1、N,Y² is selected from C (R ^Y2)_n2、N,Y³ is selected from C (R ^Y3)_n3、N,Y⁴ is selected from C (R ^Y4)_n4、N,Y⁵ is selected from C (R ^Y6)_n6、N,Y⁷ is selected from C (R ^Y7)_n7、N,Y⁸ is selected from C (N is 0, 1, 2, 3, adjacent groups in R ^Y1-R^Y8 are not linked to form a ring, or R ^Y1 and R ^Y8、R^Y1 and R ^Y2、R^Y2 and R ^Y3、R^Y3 and R ^Y4、R^Y4 and R ^Y5、R^Y5 and at least one of R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 are linked to form a ring C). More preferably, the number of N in Y ¹-Y⁸ is 0. More preferably, the number of N in Y ¹-Y⁸ is 1. More preferably, the number of N in Y ¹-Y⁸ is 2.

The number of N refers to the number selected from-n=in Y ¹-Y⁸.

Preferably, ring C is selected from R-substituted or unsubstituted C6-C20 aromatic ring, R-substituted or unsubstituted C6-C20 unsaturated carbocyclic ring, R-substituted or unsubstituted C3-C10 heteroaromatic ring.

Preferably, the ring C is selected from R-substituted or unsubstituted benzene ring, R-substituted or unsubstituted pyridine ring, R-substituted or unsubstituted indene ring, R-substituted or unsubstituted naphthalene ring, R-substituted or unsubstituted phenalene ring.

More preferably, the ring C is selected from the group consisting of an R-substituted or unsubstituted benzene ring, an R-substituted or unsubstituted indene ring, an R-substituted or unsubstituted naphthalene ring, and an R-substituted or unsubstituted phenalene ring.

When a plurality of rings C are present in the present application, each ring C may be the same or different.

Preferably, ar ¹、Ar² is notThe radicals being selected from any of the following groups

Preferably, ar ¹、Ar² is notThe group is selected from any one of the following groups:

Preferably, R ^X1-R^X6、R^X1'-R^X6' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted: one or a combination of a plurality of phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl and 9, 9-dimethylfluorenyl;

preferably, R ^Y1-R^Y8、R^Y1'-R^Y8' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-dimethylfluorenyl, or a combination of several thereof.

Preferably, each R is independently selected from one or a combination of several of deuterium, halogen, cyano, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl and 9, 9-dimethylfluorenyl.

Preferably, one of Ar ¹、Ar² is selected fromTime,Directly linked to dibenzofuran, e.g. Ar ¹ is selected fromIn the case of the formula (1) beingL ² is selected from the group consisting of a bond, a C6-C12 aryl, a C3-C10 heteroaryl; when Ar ² is selected fromIn the case of the formula (1) beingL ¹ is selected from the group consisting of a bond, a C6-C12 aryl, a C3-C10 heteroaryl.

Preferably, ar ¹、Ar² is notThe group is selected from: phenyl, naphthyl, phenanthryl, anthracyl,A group, pyrenyl, benzopyrene, phenyl substituted anthracenyl, pyridinyl, bipyridyl, terpyridyl, pyrimidinyl, phenyl substituted pyrimidinyl, diphenyl substituted pyrimidinyl, naphthyl substituted pyrimidinyl, phenanthryl substituted pyrimidinyl, anthracenyl substituted pyrimidinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl substituted carbazolyl, carbolinyl, pyridinyl substituted carbolinyl.

Preferably, ar ¹、Ar² is notThe group is selected from:

Preferably, each L ¹,L² is independently selected from the group consisting of a bond, a C6-C12 aryl, a C3-C10 heteroaryl.

Preferably, each L ¹,L² is independently selected from the group consisting of a linkage, phenylene, naphthylene, and pyridylene.

Preferably, R ¹、R² is each independently selected from the group consisting of C6-C12 aryl, C3-C10 heteroaryl.

Preferably, R ¹、R² is each independently selected from the group consisting of C6-C12 aryl.

Preferably, R ¹、R² is selected from phenyl.

Preferably, the compound is one of the following compounds 01 to 228:

the OLED luminescent compound is applied as an N-type charge generation layer material.

The invention provides an organic electroluminescent element, which comprises a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises the OLED luminescent compound.

Preferably, the organic layer comprises at least two light emitting units, a charge generation layer is arranged between the light emitting units, the charge generation layer comprises an N-type charge generation layer and a P-type charge generation layer, and the N-type charge generation layer comprises the OLED light emitting compound.

The N-type charge generating layer containing the OLED light-emitting compound of the present invention means that the OLED light-emitting compound of the present invention is contained in one N-type charge generating layer; or a plurality of N-type charge generation layers containing the heterocyclic compound of the present invention, when 2 or more N-type charge generation layers contain the OLED light-emitting compound of the present invention, the OLED light-emitting compounds are the same or different.

The laminated structure of the invention refers to N light-emitting units, wherein N is more than or equal to 2, and the number of N-type charge generation layers is N-1.

Preferably, the N-type charge generation layer includes an alkali metal or an alkaline earth metal.

The invention provides an electronic device, which comprises one or more of a display, a monitor and lighting equipment, and also comprises an organic electroluminescent element; and a control unit for driving the display device.

Compared with the prior art, the invention has the beneficial effects that:

The phosphorus-oxygen group of the OLED luminescent compound is connected with L ¹Ar¹ or L ²Ar² through dibenzofuran, and the connection position is the relative position of the same benzene ring of the dibenzofuran, so that the OLED luminescent compound has proper energy level, is used as an N-charge generation layer to facilitate the generation of charges, and is easy to transfer holes and electrons into adjacent luminescent units;

The organic electroluminescent element prepared by using the compound can realize reduced driving voltage and durable service life.

Drawings

Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to application example 1, wherein a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, an N-type charge generation layer 6, a P-type charge generation layer 7, a hole transport layer 8, a light emitting layer 9, an electron transport layer 10, an electron injection layer 11, and a second electrode layer 12, wherein 100 is a first light emitting unit, and 200 is a second light emitting unit.

Detailed Description

It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms also are intended to include the plural forms unless the context clearly indicates otherwise, and furthermore, it is to be understood that the term "comprises" and/or "comprising" when used in this specification is not limited to the disclosure of this specification.

The invention will now be further illustrated with reference to specific examples, which are given solely for the purpose of illustration and are not to be construed as limiting the invention. The test specimens and test procedures used in the following examples include those (if the specific conditions of the experiment are not specified in the examples, generally according to conventional conditions or according to the recommended conditions of the reagent company; the reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified).

Embodiments of the present invention are provided for more complete description of the present invention to those skilled in the art. The scope of the present invention is not limited to the following embodiments. These embodiments will provide a thorough and complete description of the present invention and will fully convey the concept of the invention to those skilled in the art.

As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

As used herein, the term "C1-C10 alkyl" refers to monovalent substituents derived from straight or branched chain saturated hydrocarbons having from 1 to 10 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

As used herein, the term "C3-C10 cycloalkyl (cycloalkyl)" refers to a monovalent substituent derived from a mono-or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, adamantane, and the like.

As used herein, the term "aryl of C6-C60" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such aryl groups may have a form in which two or more rings are simply flanked by each other or are fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, triphenylenyl, fluoranthracyl, perylenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, and the like.

As used herein, the term "arylene" refers to a divalent aryl radical derived from an "aryl" radical by removal of one hydrogen atom, e.g., phenyl to phenylene and naphthyl to naphthylene.

As used herein, the term "heteroaryl of C3-C60" refers to a monovalent substituent derived from a mono-or polyheterocyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring is replaced by a heteroatom, such as N, O, S, P, B or Si. Furthermore, such heteroaryl groups may have a form in which two or more rings are simply pendant from each other or are fused to each other or to an aryl group. Examples of such heteroaryl groups include, for example, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, azacarbazolyl, diazacarbazolyl, dibenzofuranyl, dibenzothienyl, and the like, to which the present invention is not limited.

As used herein, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl" group by removal of one hydrogen atom, e.g., a pyridyl group removes one hydrogen atom to a pyridylene group.

As used herein, the term "heterocyclyl" includes aromatic or non-aromatic heterocyclyl.

As used herein, the term "unsaturated carbocycle" refers to a ring atom that is carbon and contains at least one unsaturated bond, the ring comprising a single ring or two or more ring fused rings. For example tetrahydronaphthalene, 1H-phenalene

As used herein, the term "silane group" includes trimethylsilyl groups.

As used herein, the term "substituted (substituted)" refers to a group that is substituted with one or more hydrogen atoms in the compound with another substituent. The position where the substitution occurs may be a position where a hydrogen atom is substituted. That is, the position is not limited to a specific position as long as hydrogen at the position can be substituted with a substituent. For example, the carbazolyl group is specifically any of the following groups unless otherwise specified in the present specification,

The number of substitutions that occur may be one or more, and when two or more substituents are present, the two or more substituents may be the same or different.

As used in the present invention, e.gThe positions of the indicated substitutions include, but are not limited to

As used herein, the term "adjacent substituents are linked to form a ring" includes adjacent substituents on the same ring being linked to form a ring, or adjacent substituents on adjacent rings being linked to form a ring.

As used herein, the term "adjacent substituents may be linked to form a ring" including being linked to form a substituted or unsubstituted single ring, a substituted or unsubstituted fused ring, or not bonded to each other.

As used herein, the term "linkage" refers to a direct bond, e.g., L ¹ is selected from the group consisting of a linkage, then formula (1) is

As used herein, hydrogen atoms include protium, deuterium, and tritium. The compounds of the present invention may contain deuterium atoms of natural origin, or deuterium atoms may be introduced by deuterating a portion or all of the starting compounds. If deuterium atoms are introduced from the raw material, the deuteration rate may be 100%, or less than 95%, or less than 90%, or less than 80%, or 1% or more, or 5% or more, or 10% or more. Such as a deuteration ratio of not 100%, meaning a mixture of deuterated and non-deuterated compounds, or a mixture of fully deuterated and non-fully deuterated compounds, or a mixture of fully deuterated and non-deuterated compounds, respectively.

As used herein, the expression "carbon number 6 to 60" in the expression of, for example, "substituted or unsubstituted aryl group having 6 to 60 carbon atoms" means the number of carbon atoms when the aryl group is unsubstituted, excluding the number of carbon atoms of substituents when substituted, and the number of carbon atoms in the aryl group may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 … ….

As used in the present invention, the terms 1, 2, A, B, etc. are used. The above terms are used only to distinguish the constituent elements, and the nature and order of the constituent elements are not limited to the terms.

Organic electroluminescent element

The structure used for the organic electroluminescent element of the present invention is a disclosed structure comprising an anode, a cathode, and an organic layer between the anode and the cathode, the organic layer comprising a light-emitting layer, at least one layer of the organic layer comprising the compound of the present invention.

The organic layer further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

The light-emitting element of the present invention may emit fluorescence or phosphorescence or a combination thereof, and may emit light singly or in a series of a plurality of light-emitting units.

The simple light emitting element is exemplified by, but not limited to,

(1) Hole transport layer/fluorescent light emitting layer/electron transport layer;

(2) Hole transport layer/phosphorescent light emitting layer/electron transport layer;

(3) A hole transport layer/a first fluorescent light emitting layer/a second fluorescent light emitting layer/an electron transport layer;

(4) A hole transport layer/a first phosphorescent light emitting layer/a second phosphorescent light emitting layer/an electron transport layer;

(5) Hole transport layer/fluorescent light emitting layer/spacer layer/phosphorescent light emitting layer/electron transport layer;

(6) Hole transport layer/electron blocking layer/fluorescent light emitting layer/electron transport layer;

(7) Hole transport layer/electron blocking layer/fluorescent light emitting layer/hole blocking layer/electron transport layer;

(8) Hole transport layer/electron blocking layer/phosphorescent light emitting layer/electron transport layer;

(9) Hole transport layer/electron blocking layer/phosphorescent light emitting layer/hole blocking layer/electron transport layer;

(10) Hole injection layer/hole transport layer/phosphorescent light emitting layer/electron transport layer/electron injection layer;

(11) A hole injection layer/a hole transport layer/a fluorescent light emitting layer/an electron transport layer/an electron injection layer;

(12) A hole injection layer/a hole transport layer/an electron blocking layer/a phosphorescent light emitting layer/an electron transport layer/an electron injection layer;

(13) A hole injection layer/a hole transport layer/an electron blocking layer/a fluorescent light emitting layer/an electron transport layer/an electron injection layer;

The above-described phosphorescent/fluorescent light-emitting layers may each emit light of a different color.

The tandem organic electroluminescent element may be an anode, a first light-emitting unit, an intermediate layer, a second light-emitting unit, or a cathode, and the intermediate layer may be generally referred to as a charge generation layer, an electron extraction layer, a connection layer, or the like.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic electroluminescent device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers are manufactured by using a compound comprising the structure of formula (1).

As the cathode material, a material having a low work function is generally used to promote electron injection into the organic material layer.

The hole injection layer is a layer that injects holes from an electrode and has the ability to transport holes.

The hole transporting material is a layer that receives holes from the hole injecting layer and transports the holes to the light emitting layer, and the hole transporting material may suitably receive holes from the anode or the hole injecting layer and transfer the holes to the light emitting layer, which has high hole mobility.

The light emitting material may be a material that receives holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and combines the holes and the electrons to emit light in the visible light region. The light emitting layer material comprises a host material and a doping material.

The electron transporting material receives electrons from the electron injecting layer and transports the electrons to the layer of the light emitting layer, and the electron transporting material may receive electrons from the cathode and transfer the electrons to the material of the light emitting layer having high electron mobility.

The electron injection layer is a layer that injects electrons from the electrode.

The hole blocking layer is a layer that blocks holes from reaching the cathode.

An electron blocking layer is a layer that blocks electrons from reaching the anode.

The organic light emitting device of the present specification may be a top light emitting device, a bottom light emitting device, or a dual emission type device, depending on the materials used.

The charge generation layer refers to an intermediate layer located between the anode and the cathode in the tandem structure type device, and is a layer that generates holes and electrons by charge separation. The charge generation layer is typically formed of a P-type layer on the cathode side and an N-type layer on the anode side, and is effective for charge separation and efficient carrier transport.

The person skilled in the art can refer to the synthesis of the following compounds and to well known synthetic methods for synthesizing the compounds of the invention. The compound of the invention has a plurality of synthetic methods, the following general formula is only one synthetic method,

Z ¹ is selected from halogen (e.g., bromine, chlorine, iodine),-B(OH)₂，

Z ² is selected from halogen (e.g., bromine, chlorine, iodine),-B(OH)₂，

Z ³ is selected from H, halogen (e.g., bromine, chlorine, iodine),-B(OH)₂，

Z ⁴ is selected from H, halogen (e.g., bromine, chlorine, iodine),-B(OH)₂。

The reaction conditions are metal-containing catalysts and alkaline conditions.

The following are specific examples of the synthesis of the compounds of the present invention, but are not limited to the compounds exemplified below.

Example 1: preparation of Compound 109

(1) Synthesis of intermediate 109-1

Benzotriazole (20 g,167.9 mmol), 2, 6-dibromopyridine (40 g,167.9 mmol), cuI (32.9 g,167.9 mmol) and potassium tert-butoxide (37.7 g,335.8 mmol) were added to 60ml DMSO under a nitrogen atmosphere and the temperature was raised to 120℃for reaction for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride, dried over anhydrous sodium sulfate, and the solvent was removed. Purification was performed by column chromatography (developing solvent: n-hexane: ethyl acetate=25:1). Thus, intermediate 109-1 was obtained as a white solid (22 g, yield 48%).

LC-MS(APCI)：275.04(M+H⁺).

(2) Synthesis of intermediate 109-2

100G of polyphosphoric acid, 50g of phosphoric acid and 100ml of dichlorobenzene were charged into a 1000ml reaction flask, the temperature was slowly raised, when the temperature was raised to 110 ℃, intermediate 109-1 (20 g) was slowly added in portions, the temperature was then raised to 140 ℃, and after reacting for 8 hours, the reaction solution was cooled to room temperature. The reaction solution was poured into 10% sodium hydroxide solution and ph=9 was adjusted. In the alkali regulating process, the temperature is controlled between 40 ℃ and 80 ℃. After completion of the alkali adjustment, the reaction solution was extracted with methylene chloride and dried over anhydrous sodium sulfate, followed by removal of the solvent. Purification was performed by column chromatography (developing solvent: n-hexane: ethyl acetate=10:1). Thus, intermediate 109-2 was obtained as a white solid (7 g, yield 35%).

LC-MS(APCI)：247.02(M+H⁺).

(3) Synthesis of intermediate 109-3

100Ml of chlorobenzene, 2-iodopyridine (6.4 g,31.3 mmol), cuI (5.6 g,28.5 mmol), 1, 10-phenanthroline (anhydrous) (5.1 g,28.5 mmol) and potassium carbonate (7.9 g,56.9 mmol) were added under a nitrogen atmosphere, and the temperature was raised to 140℃for reaction for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride, dried over anhydrous sodium sulfate, and the solvent was removed. Purification was performed by column chromatography (developing solvent: n-hexane: dichloromethane=4:1). Thus, intermediate 109-3 was obtained as a white solid (8 g, yield 87%).

LC-MS(APCI)：324.01(M+H⁺).

(4) Synthesis of intermediate 109-4

4-Bromo-1-chloro-dibenzofuran (15 g,53.6 mmol), diphenylphosphino (13 g,64.3 mmol), 1, 3-bis [ (diphenylphosphino) propane ] dichloro-nickel (II) (1.5 g,2.7 mmol) and potassium phosphate (22.7 g,107.2 mmol) were added to 150ml of 1, 4-dioxane under nitrogen atmosphere, and the mixture was heated to 110℃for reaction. After the completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride, dried over anhydrous sodium sulfate, and the solvent was removed. Purification was performed by column chromatography (developing solvent: n-hexane: dichloromethane=2:1). Thus, intermediate 109-4 was obtained as a white solid (16 g, yield 74%).

LC-MS(APCI)：403.17(M+H⁺).

(5) Synthesis of intermediate 109-5

150Ml of 1, 4-dioxane, 1-bis (diphenylphosphine) dicyclopentadienyl iron palladium dichloride (1.4 g,2.0 mmol) and potassium acetate (7.8 g,79.6 mmol) were added to the reaction mixture under a nitrogen atmosphere, followed by heating to 110 ℃. After the completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride, concentrated and dried, and purified by column chromatography (developing solvent: methylene chloride). Concentration gave a solid, which was slurried with n-hexane, thereby obtaining intermediate 109-5 as a white solid (18 g, yield 92%).

LC-MS(APCI)：495.32(M+H⁺).

(6) Synthesis of Compound 109

Under nitrogen atmosphere, intermediate 109-3 (8 g,24.8 mmol), intermediate 109-5 (13.5 g,27.2 mmol), bis (triphenylphosphine palladium dichloride (2.2 g,3.1 mmol) and potassium carbonate (6.8 g,49.5 mmol) were added to 60ml of tetrahydrofuran 30ml of water and warmed to 80 ℃ for reaction.

LC-MS(APCI)：612.34(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.69–8.61(m,2H),8.60–8.52(m,2H),8.47(dd,1H),8.41(d,1H),8.34(dd,1H),8.16(dt,1H),7.98–7.90(m,1H),7.80–7.66(m,5H),7.63–7.45(m,8H),7.39(td,1H),7.31–7.22(m,2H),7.17(dd,1H).

Example 2: preparation of Compound 145

(1) Synthesis of intermediate 145-1

Under a nitrogen atmosphere, 60ml of tetrahydrofuran, 20ml of water, and 5g of 9-bromo-1-chlorodiphenylfuran (5 g,17.8 mmol), 9-phenanthreneboronic acid (4.3 g,19.5 mmol), and tetrakis triphenylphosphine palladium (0.41 g,0.36 mmol) and potassium carbonate (4.9 g,35.5 mmol) were added, and the mixture was heated to reflux for 6 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride, dried over anhydrous sodium sulfate, and the solvent was removed. Purification to solid was carried out by column chromatography (developing solvent: n-hexane). Further, beating with ethanol was performed, thereby obtaining a white solid (6 g, yield 88%) of intermediate 145-1.

LC-MS(APCI)：379.18(M+H⁺).

(2) Synthesis of Compound 145

Intermediate 145-1 (24.35 g,0.0643 mol), diphenyloxyphosphorus (13.64 g,0.0675 mol), bis (triphenylphosphine) palladium (II) chloride (1.75 g,2.49 mmol) and potassium carbonate (27.29 g, 0.197mol) were added to 450ml of N' N-dimethylformamide under a nitrogen atmosphere and refluxed for 6 hours. The reaction solution was cooled to room temperature, and ethyl acetate was added. The obtained organic layer was washed three times with saturated brine, and the solvent was removed after drying over anhydrous sodium sulfate. The obtained solid was purified by column chromatography (developing solvent: ethyl acetate: n-hexane=1:10), and then crystallized (toluene). Thus, a white solid (12.1 g, yield 34.6%) of compound 145 was obtained.

MS(APCI):545.32(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.83(dd,2H),8.58–8.53(m,1H),7.97(dd,1H),7.91(s,1H),7.84–7.47(m,16H),7.40–7.35(m,2H),7.24–7.15(m,2H).

Example 3: synthesis of Compound 193

To the reaction flask were added intermediate 109-5 (10 g,20.23 mmol), 1-bromo-4-phenylnaphthalene (6 g,21.28 mmol), tetrakis triphenylphosphine palladium (0.5 g,0.43 mmol), potassium carbonate (5.6 g,40.52 mmol), 70ml toluene, 30ml ethanol, 30ml water, and reacted at 95℃for 8h. After the completion of the reaction, the reaction mixture was extracted with methylene chloride, and the solvent was removed after drying over anhydrous sodium sulfate. Recrystallisation from ethyl acetate (purification). This gave compound 193 (6 g, 52.03% yield) as a white solid.

LC-MS(APCI)：571.48(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.45(dt,1H),7.93(dt,1H),7.78–7.67(m,4H),7.58(s,2H),7.56–7.36(m,14H),7.35–7.27(m,3H),7.16–7.05(m,2H).

Example 4: synthesis of Compound 197

Under a nitrogen atmosphere, intermediate 109-5 (5.45 g, 0.01100 mol), 3-bromobenzo [ e ] pyrene (3.48 g,0.0105 mol), tetrakis triphenylphosphine palladium (0.24 g,0.21 mmol) and potassium carbonate (2.90 g,0.021 mol) were added to 60ml toluene, 30ml ethanol, and 30ml water, and refluxed for 6 hours. The reaction solution was cooled to room temperature and filtered to obtain crude solid. The solid was slurried with tetrahydrofuran. Thus, compound 197 (4.5 g, yield 69%) was obtained as an off-white solid.

MS(APCI):619.45(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ9.07(d,1H),9.00(dd,1H),8.93(tdd,2H),8.58(dt,1H),8.24–8.18(m,2H),8.10(t,1H),7.99(d,1H),7.92–7.78(m,7H),7.67–7.51(m,7H),7.41–7.37(m,2H),7.28–7.19(m,2H).

Example 5: synthesis of Compound 204

To the reaction flask were added intermediate 109-5 (10 g,20.23 mmol), 1-bromobenzofuran (5.2 g,2.1 mmol), tetrakis triphenylphosphine palladium (0.5 g,0.43 mmol), potassium carbonate (5.6 g,40.52 mmol), 105ml toluene, 45ml ethanol, 45ml water, and reacted at 95℃for 8h. After the completion of the reaction, the reaction mixture was extracted with methylene chloride, and the solvent was removed after drying over anhydrous sodium sulfate. With n-hexane: tetrahydrofuran was recrystallized (purified). Thus, compound 204 (8 g, yield 70.80%) was obtained as a white solid.

LC-MS(APCI)：535.41(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.53–8.43(m,1H),7.66(s,5H),7.47(s,10H),7.36–7.23(m,3H),7.18–7.07(m,2H),6.97–6.84(m,2H).

Example 6: synthesis of Compound 196

Intermediate 109-5 (5.8 g,0.019 mol), 5.6g potassium carbonate (0.040 mol), 1.2g palladium tetraphenyl phosphine (0.001 mol) were dissolved in 150ml toluene, 50ml ethanol, 50ml water under an atmosphere of N ₂. Heating to 80 ℃ for reaction. Separating liquid after the reaction is finished, and mixing the organic phase with silica gel after drying. Column chromatography (n-hexane: dichloromethane: tetrahydrofuran=volume ratio 10:10:1) and toluene beating gave product compound 196 (3.4 g, yield 30.2%).

LC-MS(APCI)：595.43(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.87–8.85(d,1H),8.79(s,1H),8.77–8.74(d,1H),8.68–8.66(d,1H),8.50–8.48(d,1H),8.05–8.02(d,1H),7.98–7.96(d,1H),7.77–7.71(m,4H),7.69–7.67(d,2H),7.64–7.58(m,2H),7.56–7.53(m,3H),7.49–7.45(m,5H),7.32–7.27(m,2H),7.17–7.10(m,2H).

Example 7: synthesis of Compound 146

Step one: to a 250ml four-necked flask, intermediate 109-4 (10.0 g,24.83 mmol), 1-pyrenylboronic acid (6.6 g,26.82 mmol), potassium carbonate (6.8 g,49.65 mmol), [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride (900 mg,1.24 mmol), toluene (60 ml), ethanol (20 ml) and water (20 ml) were successively added, followed by a reflux reaction for 6 hours after nitrogen substitution. After the reaction is finished, tetrahydrofuran is used for: dichloromethane = volume ratio 1:10 on a silica gel flash column, concentrated and recrystallized from toluene to give compound 146 (9.5 g, yield 67.34%).

LC-MS(APCI):[M+H]⁺＝569.41

¹H NMR(400MHz,Methylene Chloride-d2)δ8.57(dt,1H),8.35(d,1H),8.28(dd,1H),8.25–8.15(m,4H),8.10–8.00(m,2H),7.91(d,1H),7.83(dd,5H),7.67–7.51(m,6H),7.43–7.34(m,2H),7.27–7.19(m,2H).

Example 8: synthesis of Compound 148

Step one: to a 250ml four-necked flask, intermediate 109-4 (10.0 g,24.83 mmol), (10-phenylanthracen-9-yl) boric acid (8.0 g,26.82 mmol), potassium carbonate (6.8 g,49.65 mmol), [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (900 mg,1.24 mmol), toluene (60 ml), ethanol (20 ml), water (20 ml) were successively added, and the mixture was replaced with nitrogen and then refluxed for 6 hours. After the reaction is finished, tetrahydrofuran is used for: dichloromethane = volume ratio 1:10 on a silica gel flash column, concentrated and recrystallized from toluene to give compound 148 (10.6 g, yield 68.83%).

LC-MS(APCI):[M+H]⁺＝621.48

¹H NMR(400MHz,Methylene Chloride-d2)δ8.57(ddd,1H),7.91–7.82(m,4H),7.79–7.73(m,2H),7.68–7.47(m,14H),7.41–7.18(m,8H).

Example 9: synthesis of Compound 198

Under the nitrogen environment, sequentially adding into four bottles: intermediate 109-5 (10 g,20.2 mmol), 3-chloro-9-phenyl-9-hydrogen-carbazole (5.6 g,20.2 mmol), tetrakis (triphenylphosphine) palladium (0.6 g,0.5 mmol), potassium carbonate (10.6 g,73.8 mmol) and tetrahydrofuran with 100ml water (volume ratio 3:1). Reflux was continued for 2h at elevated temperature, cooled to room temperature, filtered, and the filtrate was concentrated under reduced pressure, and slurried with 100ml of toluene to give compound 198 (12 g, yield 97.52%).

LC-MS(APCI):[M+H]⁺＝610.19

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.62(dd,1H),8.45(ddd,1H),8.16(dt,1H),7.90(dd,1H),7.71–7.62(m,4H),7.59–7.48(m,9H),7.46–7.33(m,8H),7.29–7.20(m,1H),7.12(ddd,1H),7.04(dd,1H).

Example 10: synthesis of Compound 206

Under the nitrogen environment, sequentially adding into four bottles: intermediate 109-5 (10 g,20.2 mmol), 2- (4-bromonaphthalen-1-yl) pyrimidine (5.77 g,20.2 mmol), tetrakis (triphenylphosphine) palladium (0.6 g,0.5 mmol), potassium carbonate (4.19 g,30.34 mmol) and tetrahydrofuran with 100ml of water (3:1). Reflux reaction at elevated temperature for 2h, standing for delamination after reaction, discarding water phase, concentrating organic phase under reduced pressure, pulping with toluene 100ml to obtain compound 206 solid (9.5 g, yield: 82.13%).

LC-MS(APCI):[M+H]⁺＝573.6

¹H NMR(400MHz,Methylene Chloride-d₂)δ9.02(d,2H),8.79(dt,1H),8.59(dt,1H),8.22(d,1H),7.88–7.79(m,5H),7.74(ddd,1H),7.69–7.62(m,2H),7.58(ddd,6H),7.50–7.40(m,4H),7.28–7.17(m,2H).

Example 11: synthesis of Compound 190

Under an atmosphere of N ₂, 6-bromo-2, 2':6',2' -dipyridine (7 g,0.023 mol), intermediate 109-5 (12.2 g,0.025 mol), 6.2g potassium carbonate (0.046 mol), 0.8g diphenylphosphine palladium dichloride (0.001 mol) are dissolved in 150ml toluene, 50ml ethanol and 50ml water, the temperature is raised to 80 ℃ for reaction, the reaction is completed, the liquid is separated, the organic phase is dried, and the silica gel is stirred. Column chromatography (n-hexane: dichloromethane: tetrahydrofuran=volume ratio 10:10:1) afforded product compound 190 (5.8 g, yield 41.5%).

LC-MS(APCI)：600.47(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.64–8.58(m,3H),8.56–8.50(m,3H),8.43–8.40(m,2H),8.05–8.01(t,1H),7.92–7.88(t,1H)7.84–7.80(m,1H),7.69–7.63(m,4H),7.61–7.58(d,1H),7.54–7.49(m,2H),7.46–7.38(m,5H),7.30–7.26(m,1H),7.18–7.09(m,2H)

Example 12: synthesis of Compound 186

Step one: under the nitrogen environment, sequentially adding into four bottles: 4-bromo-1-chlorodibenzofuran (10 g,35.52 mmol), diphenylphosphino (7.9 g,39.07 mmol), tetrakis (triphenylphosphine) palladium (0.82 g,0.71 mmol), potassium carbonate (9.82 g,71.04 mmol) and tetrahydrofuran (100 ml), and after the reaction was heated and refluxed for 8 hours, the reaction solution was passed through a silica gel funnel, the filtrate was concentrated under reduced pressure, and slurried with 50ml of methanol to give intermediate 186-1 solid (12.8 g,31.78 mmol).

LC-MS(APCI):[M+H]⁺＝403.81

Step two: under the nitrogen environment, sequentially adding into four bottles: intermediate 186-1 (12.8 g,31.78 mmol), 9-phenanthreneboronic acid (7.41 g,33.37 mmol), bis (triphenylphosphine) palladium dichloride (0.44 g,0.63 mmol), potassium carbonate (6.59 g,47.66 mmol) and tetrahydrofuran (100 ml), water (30 ml). Reflux reaction at elevated temperature for 3h, reaction mixture standing for delamination, discarding water phase, organic phase passing through silica gel funnel, concentrating filtrate under reduced pressure, pulping with 50ml of n-hexane to obtain compound 186 (14.68 g, yield: 84.83%).

LC-MS(APCI):[M+H]⁺＝545.59

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.83–8.73(m,2H),7.92–7.75(m,8H),7.70(ddd,1H),7.61(dtd,2H),7.58–7.50(m,2H),7.50–7.42(m,5H),7.32(ddt,2H),7.19(ddd,1H),6.74(ddd,1H),6.49(ddd,1H).

Example 13: synthesis of Compound 159

Diphenyl (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) dibenzo [ b, d ] furan-1-yl) phosphine oxide (12.50 g,0.0265 mol), 2-bromobenzo [9,10] phenanthrene (7.75 g,0.0252 mol), tetrakis triphenylphosphine palladium (0.24 g,0.21 mmol) and potassium carbonate (6.97 g,0.0504 mol) were added to 150ml toluene, 70ml ethanol, and 60ml water under nitrogen atmosphere, and refluxed for 5 hours. The reaction solution was cooled to room temperature and filtered to obtain crude solid. The solid was toluene beaten. Thus, compound 159 was obtained as a white solid (11.5 g, yield 76%).

LC-MS(APCI):595.85(M+H⁺).Calcd for C₄₂H₂₇O₂P.

¹H NMR(400MHz,Methylene Chloride-d₂)δ9.25(d,1H),8.85(d,1H),8.81–8.69(m,4H),8.60(dd,1H),8.24(dd,1H),7.81–7.70(m,9H),7.67–7.58(m,3H),7.56–7.45(m,5H),7.28–7.16(m,2H).

The following examples of application of the OLED light-emitting compounds according to the present invention in the preparation of organic electroluminescent elements are further described.

Application example 1

The present embodiment provides an organic electroluminescent device, as shown in fig. 1, including a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, an N-type charge generation layer 6, a P-type charge generation layer 7, a hole transport layer 8, a light emitting layer 9, an electron transport layer 10, an electron injection layer 11, and a second electrode layer 12, which are stacked, wherein 100 is a first light emitting unit, and 200 is a second light emitting unit.

The specific device structure is as follows:

ITO(100nm)/NPD:F4-TCNQ(10％)(10nm)/NPD(120nm)/BH:BD(3％)(20nm)/

TmPyPB(10nm)/Bphen:Li(2％)(10nm)/NPD:F4-TCNQ(10％)(20nm)/NPD(20nm)/BH:BD(3％)(20nm)/Alq₃(10nm)/LiF(0.5nm)/Al(200nm).

the preparation process of the device comprises the following steps:

The bottom emission glass substrate used in this example was purchased from Guangdong Xinli display technology Co., ltd, and 100nm ITO was used as the first electrode layer 1. Firstly, the bottom luminescent glass substrate is cleaned by using ITO cleaning agent, deionized water and isopropanol in sequence, and then baked for 30 minutes at 180 ℃ to be dried.

Then, the bottom emission glass substrate was placed in an evaporation chamber, and organic layers were sequentially deposited on the ITO anode by thermal vacuum evaporation at a rate of 0.2-2 Angstrom/second under a vacuum of about 10 ^-8 Torr. Wherein F4-TCNQ (mass content 10%) was incorporated into NPD to form a thickness of 10nm as a hole injection layer. NPD is formed to a thickness of 120nm as a hole transporting layer, a pyrene dopant 1,6-bis (diphenylamino) pyrene having a mass content of 3% is doped on an anthracene host ADN (9, 10-di (naphthalene-2-yl-) anthracene), a blue light emitting layer having a thickness of 20nm is formed, tmPyPB is formed to a thickness of 10nm as a first electron transporting layer, li having a mass content of 2% is doped in BPhen (4, 7-Diphenyl-1, 10-phenanthrine), an N-type charge generating layer 6 having a thickness of 10nm is formed, F4-TCNQ having a mass content of 10% is doped on NPD, a P-type charge generating layer having a thickness of 20nm is formed, NPD is formed to a hole transporting layer having a thickness of 20nm, a pyrene dopant 1,6-bis (diphenylamino) having a mass content of 3% is doped on an anthracene host ADN (9, 10-di (naphthalene-2-yl-) anthracene) is formed, an electron transporting layer having a thickness of 34 nm is formed, and an Alum- (2-ethyl-) is formed as an electron transporting layer having a thickness of 34 nm, and an Alum-20.0.3 nm is formed as an electron transporting layer.

Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, designated as organic electronic element 1 (comparative example).

Contrast structure

Bphen(4,7-Diphenyl-1,10-phenanthroline)

Examples and comparative examples

REF-2 synthesis method:

2, 8-dibromodibenzofuran (30 g,92.03 mmol), 9-phenanthreneboronic acid (10.7 g,48.18 mmol), potassium carbonate (25.4 g,184.05 mmol) and tetraphenylpalladium phosphate (2.12 g,1.84 mmol) were charged into a four-port reaction flask under N ₂ atmosphere, followed by adding 556ml of a toluene/ethanol/water mixed solvent. The reaction was heated to 80 ℃ overnight. And (3) detecting by TLC the next day, checking by LC-MS to confirm that the 9-phenanthreneboronic acid is reacted, stopping heating, and cooling to room temperature. 500ml of water and 500ml of ethyl acetate were added to extract the reaction solution, and the separated organic phase was washed three more times with water, dried over anhydrous sodium sulfate and filtered, and EA was removed by rotary evaporation to give 45g of crude product. After purification by column chromatography, 30g of white solid was obtained. (purification by chromatography column is not effective, raw materials, products and impurities are not separated) and are directly used in the next step.

LC-MS(APCI)：424.32(M+H⁺).Calcd for C₂₆H₁₅BrO

2-Bromo-8- (9-phenanthryl) dibenzofuran (30 g,91.46 mmol), diphenylphosphino (28.6 g,105.53 mmol), potassium phosphate (30.1 g,217.78 mmol) and 1, 3-bis (diphenylpropane) nickel dichloride (2.3 g,4.26 mmol) were added to a four port reaction flask under N ₂ atmosphere, then N, N-dimethylformamide (500 ml) was added, heated to 150℃and after 3h of reaction, the sample was plated onto LC-MS, after confirming the end of the reaction, heating was stopped, cooled to room temperature, 500ml of water was added, 500ml of ethyl acetate was extracted from the reaction solution, the separated organic phase was washed three times with water, dried over anhydrous sodium sulfate, stirred with 80g of silica gel, and purified by column chromatography on 200-300 mesh silica gel to give a viscous solid 20g with a purity of 98.1% yield of 40.2%.

LC-MS(APCI)：545.39(M+H⁺).

¹H NMR(400MHz,Methylene Chloride-d₂)δ8.77–8.71(m,1H),8.70–8.65(m,1H),8.25(ddd,1H),8.03(dd,1H),7.83(ddd,2H),7.75–7.52(m,12H),7.51–7.34(m,7H).

Charge generation layer an N-type charge generation layer 6 was prepared using the compound 109 prepared in example 1 of the present invention instead of Bphen material, and an organic electronic device 2 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 145 prepared in example 2 of the present invention instead of Bphen material, and an organic electronic device 3 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 193 prepared in example 3 of the present invention instead of Bphen material, and an organic electronic device 4 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 197 prepared in example 4 of the present invention instead of Bphen material, and an organic electronic device 5 was produced in the same manner.

An N-type charge generation layer 6 was prepared using the compound 204 prepared in example 5 of the present invention instead of Bphen material, and an organic electronic device 6 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 196 prepared in example 6 of the present invention instead of Bphen material, and an organic electronic device 7 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 146 prepared in example 7 of the present invention instead of Bphen material, and an organic electronic device 8 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 148 prepared in example 8 of the present invention instead of Bphen material, and an organic electronic device 9 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 198 prepared in example 9 of the present invention instead of Bphen material, and an organic electronic device 10 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 206 prepared in example 10 of the present invention instead of Bphen material, and an organic electronic device 11 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 190 prepared in example 11 of the present invention instead of Bphen material, and an organic electronic device 12 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 186 prepared in example 12 of the present invention instead of Bphen material, and an organic electronic element 13 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared using the compound 159 prepared in example 13 of the present invention instead of Bphen material, and an organic electronic device 14 was fabricated in the same manner.

An N-type charge generation layer 6 was prepared by replacing Bphen material with REF-2, and an organic electronic element 15 was fabricated in the same manner.

Evaluation of organic electroluminescent device

The service life testing method comprises the following steps: the obtained organic electroluminescent device was subjected to voltage so that the current density became 30mA/cm ², and the time (LT 95 (unit: hours)) until the luminance became 95% with respect to the initial luminance was measured.

The drive voltage was measured at a current density of 15mA/cm ².

The percent life results of each example are given as 100% life results of the organic electronic element 1 (comparative example), and are specifically shown in table 1.

Organic electronic element 1: the driving voltage was 7.07V and LT95 was 58 hours.

Organic electronic element 2: the driving voltage was 6.94V and the LT95 of the device prepared with compound 109 as N-CGL was 220% of that obtained with Bphen as N-CGL.

Organic electronic element 3: the driving voltage was 7.00V and device LT95, prepared with Compound 145 as the N-CGL, was 162% of that obtained with Bphen as the N-CGL. And so on.

TABLE 1

The organic electroluminescent element prepared by the compound of the present invention has not only a reduced driving voltage but also a long service life compared with the known compounds Bphen and REF-2. Compared with the structure of REF-2, the phosphorus-oxygen group and Ar group in the compound are on the same benzene ring of the dibenzofuran, and the charge generation and migration capacity of the compound is superior to that of the phosphorus-oxygen group and Ar group on different benzene rings of the dibenzofuran.

In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.

The OLED light-emitting compound and the organic electroluminescent device comprising the same provided by the present invention are described in detail above. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims

1. An OLED light-emitting compound characterized by: the compound has a structure shown in a formula (1),

One of Ar ¹、Ar² is selected fromR ¹、R² is independently selected from R substituted or unsubstituted C6-C30 aryl, R substituted or unsubstituted C3-C30 heteroaryl; the other is selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl,

2. The OLED light-emitting compound according to claim 1, wherein: ar ¹、Ar² is notThe radicals being selected fromOr

The number of linkages in X ¹-X⁶ is 0 or 1,O is 0 or 1, the number of S is 0 or 1, the number of N is 0,1, 2, 3, NR ^X1' is 0 or 1, NR ^X2' is 0 or 1, NR ^X3' is 0 or 1, NR ^X4' is 0 or 1, NR ^X5' is 0 or 1, NR ^X6' is 0 or 1, R ^X1-R^X6、R^X1'-R^X6' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C1-C10 alkyl, R substituted or unsubstituted C3-C10 cycloalkyl, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl,

The number of linkages in Y ¹-Y⁸ is 0 or1,O is 0 or1, the number of S is 0 or1, the number of N is 0,1, 2, 3, the number of NR ^Y1' is 0 or1, the number of NR ^Y2' is 0 or1, the number of NR ^Y3' is 0 or1, the number of NR ^Y4' is 0 or1, the number of NR ^Y5' is 0 or1, the number of NR ^Y6' is 0 or1, the number of NR ^Y7' is 0 or1, the number of NR ^Y8' is 0 or1, R ^Y1-R^Y8、R^Y1'-R^Y8' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted C1-C10 alkyl, R substituted or unsubstituted C3-C10 cycloalkyl, R substituted or unsubstituted C6-C60 aryl, R substituted or unsubstituted C3-C60 heteroaryl,

Adjacent R ^Y1-R^Y8 are not linked, or at least one pair of R ^Y1 and R ^Y8、R^Y1 and R ^Y2、R^Y2 and R ^Y3、R^Y3 and R ^Y4、R^Y4 and R ^Y5、R^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 are linked to form a ring C selected from the group consisting of an R substituted or unsubstituted aromatic ring of C6-C60, an R substituted or unsubstituted unsaturated carbocyclic ring of C6-C30, an R substituted or unsubstituted heteroaromatic ring of C3-C30.

3. The OLED light-emitting compound according to claim 2, wherein:

In the formula (2), X ¹ is selected from CR ^X1、N,X², CR ^X2、N,X³ is selected from CR ^X3、N,X⁴, CR ^X4、N,X⁵ is selected from CR ^X5、N,X⁶ is selected from CR ^X6 and N, and the number of N in X ¹-X⁶ is 0, 1,2 and 3.

4. The OLED light-emitting compound according to claim 2, wherein:

In formula (3), Y ¹ is selected from a bond, Y ⁴ is selected from C (R ^Y4)_n4、O、S、NR^Y4',Y² is selected from N, C (R ^Y2)_n2,Y³ is selected from N, C (R ^Y3)_n3,Y⁵ is selected from N, C (R ^Y5)_n5,Y⁶ is selected from N, C (R ^Y6)_n6,Y⁷ is selected from N, C (R ^Y7)_n7,Y⁸ is selected from N, C (the number of N in R ^Y8)_n8,Y²-Y³、Y⁵-Y⁸ is 0 or 1 or 2, R ^Y2-R^Y3、R^Y5-R^Y8 is not linked to form a ring, or at least one pair of R ^Y2 and R ^Y3、R^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 is linked to form a ring C).

5. The OLED light-emitting compound according to claim 2, wherein:

In formula (3), Y ¹ is selected from O, S, N, NR ^Y1',Y² from O, S, N, NR ^Y2'、C(R^Y2)_n2,Y³ from a bond, Y ⁴ is selected from O, S, N, NR ^Y4',Y⁵ from N, C (R ^Y5)_n5,Y⁶ is selected from N, C (R ^Y6)_n6,Y⁷ is selected from N, C (R ^Y7)_n7,Y⁸ is selected from N, C (N is 0, 1,2, o is 0 or 1 in R ^Y8)_n8,Y¹-Y²、Y⁴-Y⁸, s is 0 or 1, R ^Y5-R^Y8 is not linked to form a ring, or at least one pair of R ^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8 is linked to form a ring C).

6. The OLED light-emitting compound according to claim 2, wherein:

In formula (3), Y ¹ is selected from C (R ^Y1)_n1、N,Y² is selected from C (R ^Y2)_n2、N,Y³ is selected from C (R ^Y3)_n3、N,Y⁴ is selected from C (R ^Y4)_n4、N,Y⁵ is selected from C (R ^Y6)_n6、N,Y⁷ is selected from C (R ^Y7)_n7、N,Y⁸ is selected from C (N is 0, 1,2,3, adjacent groups in R ^Y1-R^Y8 are not linked to form a ring, or at least one group of R ^Y1 and R ^Y2、R^Y2 and R ^Y3、R^Y3 and R ^Y4、R^Y4 and R ^Y5、R^Y5 and R ^Y6、R^Y6 and R ^Y7、R^Y7 and R ^Y8、R^Y1 and R ^Y8 are linked to form a ring C).

7. The OLED light-emitting compound according to any one of claim 2, wherein: the ring C is selected from R-substituted or unsubstituted benzene ring, R-substituted or unsubstituted pyridine ring, R-substituted or unsubstituted indene ring, R-substituted or unsubstituted naphthalene ring, R-substituted or unsubstituted phenalene ring.

8. The OLED light-emitting compound according to claim 2, wherein: ar ¹、Ar² is notThe radicals being selected from any of the following groups

9. The OLED light-emitting compound according to claim 2, wherein: ar ¹、Ar² is notThe radicals being selected from any of the following groups

10. The OLED light-emitting compound according to claims 2-9, wherein:

R ^X1-R^X6、R^X1'-R^X6' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted: one or a combination of a plurality of phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl and 9, 9-dimethylfluorenyl;

R ^Y1-R^Y8、R^Y1'-R^Y8' are each independently selected from hydrogen, deuterium, halogen, cyano, R substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-dimethylfluorenyl, or a combination of several thereof.

11. The OLED light-emitting compound according to claim 1, wherein: each R is independently selected from one or a combination of more of deuterium, halogen, cyano, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, bipyridyl, terpyridyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl and 9, 9-dimethylfluorenyl.

12. The OLED lighting compound according to claim 1, wherein Ar ¹、Ar² is notThe group is selected from:

13. the OLED light-emitting compound according to claim 1 or 12, wherein the compound is one of the following compounds 1 to 228:

14. An organic electroluminescent element comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, characterized in that: the organic layer comprises the OLED light-emitting compound according to any one of claim 1.

15. The organic electroluminescent element according to claim 14, wherein: the organic layer comprises at least two light emitting units, a charge generation layer is arranged between the light emitting units, the charge generation layer comprises an N-type charge generation layer and a P-type charge generation layer, and the N-type charge generation layer is selected from the OLED light emitting compounds of claim 1.

16. An electronic device comprising one or more of a display, a monitor, and a lighting apparatus, comprising the organic electroluminescent element according to claim 14.