WO2022089415A1

WO2022089415A1 - Novel boron-containing organic compound and application thereof

Info

Publication number: WO2022089415A1
Application number: PCT/CN2021/126355
Authority: WO
Inventors: 李国孟; 李熠烺; 孙磊; 徐超; 曾礼昌
Original assignee: 北京鼎材科技有限公司
Priority date: 2020-10-27
Filing date: 2021-10-26
Publication date: 2022-05-05
Also published as: CN114478594A

Abstract

The present invention relates to a compound and an application thereof. The compound has the structure as shown in formula (1). The compound provided in the present invention introduces substituted aryl groups containing N atoms in B-N resonant materials. The substituted aryl groups containing N atoms are substituted on an aromatic ring directly linked to the central B and N atoms. When the compound in the present application is applied to an organic electroluminescence device, especially to a luminescent layer material, the carrier transport and balance in the device can be effectively improved, to ensure that the device achieves excellent effects of high luminous efficiency and low starting voltage.

Description

A Novel Boron-Containing Organic Compound and Its Application

technical field

The invention relates to a boron-containing organic material, which belongs to the technical field of organic light-emitting materials, and also relates to the application of the compound in organic electroluminescent devices.

Background technique

The main way for people to obtain information is through vision, so in the process of human interaction with information, display devices are very important. Organic electroluminescent diodes (OLEDs) have many advantages such as flexibility, self-luminescence, high contrast, large size, and low power consumption, and have become one of the mainstream display devices.

Among them, red and green dyes, which are three primary colors, generally contain heavy atoms such as Ir, Pt, etc., can theoretically achieve 100% internal quantum efficiency, high electroluminescence efficiency, and low power consumption. Mainstream display devices. However, the chromaticity and lifetime of blue phosphorescent materials cannot meet the current commercial display requirements. At present, blue light devices still use traditional fluorescent materials to achieve high color purity and long device lifetime.

SUMMARY OF THE INVENTION

Recently, Japanese researchers such as Takuji Hatakeyama and Junji Kido reported a series of organic materials DABNA-1 based on B-N resonance type TADF (Thermally Activated Delayed Fluorescence) (Adv.Mater.2016,28,2777– 2781J.Mater.Chem.C, 2019,7,3082-3089), the boron atom, nitrogen atom and phenyl group of this kind of compound constitute a rigid polycyclic aromatic skeleton, so it has a high fluorescence quantum yield. Compared with traditional blue fluorescent dyes, these compounds have narrower spectrum and higher color purity. However, the rigid planar structure also leads to a large energy level difference between the singlet state and the triplet state, and the reverse intersystem crossing from the triplet state to the singlet state is slow. Short lifespan. In addition, an overly planar rigid structure often leads to unfavorable effects such as spectral broadening and redshift caused by too high doping concentration.

Konica Minolta (WO2019163625A) discloses a class of boron-containing organic materials. In this patent, the boron-containing organic material is combined with a class of fluorine-containing solvent components to be used as a class of electron transport materials, and its The compounds containing N-atom-substituted aryl groups in the patent are all B-O coordination materials. If the B-O coordination materials are connected with N-atom-substituted aryl groups, their resonance characteristics are easily broken, forming a class of D-A type materials. With a strong CT state, the emission spectrum is broadened, thus losing the narrow spectrum characteristics of boron-containing organic materials. Konica Minolta (CN109155370A) also discloses a class of boron-containing organic materials, which require a central B atom and three surrounding atoms (one of which must be N, and the other two can be O or S) Coordinate.

Existing organic electroluminescent materials still have a lot of room for improvement in terms of luminescent properties, and the industry urgently needs to develop new luminescent material systems to meet commercialization needs.

In order to solve the above-mentioned technical problems, the present invention provides a compound of general formula B with a new structure, and a kind of substituted aryl group containing N atom is introduced into the B-N resonance type material. Substituted on the aromatic ring directly connected by B atom and N atom, this type of B-N coordination material has strong self-stability, and can still maintain its own narrow spectral emission characteristics even after the aryl group containing N atom is substituted.

The present invention provides a compound of general formula, the structure of which is shown in general formula (1):

In formula (1):

The ring X, ring Y and ring Z are each independently selected from one of substituted or unsubstituted C5-C30 aromatic rings and substituted or unsubstituted C3-C30 heteroaromatic rings; further, the ring X , Ring Y and Ring Z are each independently selected from a substituted or unsubstituted C5-C14 aromatic ring, a substituted or unsubstituted C3-C14 heteroaromatic ring; further, the ring X, ring Y and Ring Z is independently selected from a substituted or unsubstituted C5-C8 aromatic ring, a substituted or unsubstituted C5-C8 heteroaromatic ring;

Most preferably, the ring X, ring Y and ring Z are each independently selected from substituted or unsubstituted benzene ring, substituted or unsubstituted furan ring, substituted or unsubstituted thiophene ring, substituted or unsubstituted naphthalene ring , a substituted or unsubstituted phenanthrene ring or a substituted or unsubstituted carbazole ring.

Ar ¹ and Ar ² are each independently selected from one of substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C3-C60 heteroaryl groups;

Ar ¹ forms a ring or does not form a ring with the adjacent ring X or ring Z, Ar ² forms a ring or does not form a ring with the adjacent ring Y or ring Z; and the ring X, ring Y, ring Z, At least one of Ar ¹ and Ar ² is substituted by a group of the structure represented by formula (G);

Preferably, one of the ring X, ring Y, ring Z, Ar ¹ and Ar ² is substituted by a group of the structure represented by the formula (G); more preferably, the ring Z is replaced by a group of the structure represented by the formula (G) replaced by the regiment;

In formula (G):

X ₁ -X ₈ are each independently selected from CR ¹ or N, and said R ¹ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, Substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted One of substituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and the R ¹ is independently connected to the connected aromatic ring Ringed or not connected to ring, and at least one of X ₁ -X ₈ is N;

n is 0 or 1, and E ¹ is selected from one of CR ² R ³ , NR ⁴ , O, S, SiR ⁵ R ⁶ ;

When n is 0, it means that E ¹ does not exist, and at this time, the two atoms connected to E ¹ in formula (G) are directly connected through a single bond;

R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted One of the C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

When the above groups have substituents, the substituents are selected from halogen, cyano, carbonyl, nitro, amino, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl group, C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C30 monocyclic aryl or fused-ring aryl, C3-C30 monocyclic heteroaryl or fused-ring heteroaryl one or a combination of at least two.

It should be noted that, unless otherwise defined below, all technical and scientific terms used herein are intended to have the same meaning as commonly understood by those skilled in the art. References to techniques used herein are intended to refer to techniques commonly understood in the art, including those variations or substitutions of equivalent techniques that would be apparent to those skilled in the art. While the following terms are believed to be well understood by those skilled in the art, the following definitions are set forth to better explain the present invention.

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

In this specification, the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent. When describing C1-30, it includes but is not limited to C1, C2, C3, C4, C3, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28, etc., and other numerical ranges will not be repeated.

The terms "comprising", "comprising", "having", "containing" or "involving" and other variations thereof herein are inclusive or open ended and do not exclude other unrecited elements or method steps.

In the present invention, the expression of chemical elements, unless otherwise specified, usually includes the concept of isotopes with the same chemical properties, such as the expression of "hydrogen", also includes the concepts of "deuterium" and "tritium" with the same chemical properties, carbon ( C) then includes ¹² C, ¹³ C, etc., and will not be repeated here.

As used herein, the terms "heterocyclyl" and "heterocycle" refer to saturated (ie, heterocycloalkyl) having at least one ring atom that is a heteroatom selected from N, O, and S and the remaining ring atoms being C ) or partially unsaturated (ie having one or more double and/or triple bonds within the ring) cyclic group.

As used herein, the terms "()arylene" and "aromatic ring" refer to an all-carbon monocyclic or fused ring polycyclic aromatic group having a conjugated pi electron system. As used herein, the terms "()heteroarylene" and "heteroaromatic ring" refer to monocyclic, bicyclic or tricyclic aromatic ring systems. As used herein, the term "aralkyl" preferably refers to an aryl or heteroaryl substituted alkyl group, wherein said aryl, heteroaryl and alkyl groups are as defined herein.

As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br or I.

The term "substituted" means that one or more (eg, one, two, three, or four) hydrogens on the designated atom are replaced by a selection from the designated group, provided that no more than the designated atom is present in the normal valences in the case and the substitutions form stable compounds. Combinations of substituents and/or variables are permissible only if such combinations form stable compounds.

If substituents are described as being "independently selected from" a group, each substituent is selected independently of the other. Thus, each substituent may be the same as or different from another (other) substituent.

As used herein, the term "one or more" means 1 or more than 1, such as 2, 3, 4, 5 or 10, under reasonable conditions.

Unless indicated, as used herein, the point of attachment of a substituent can be from any suitable position on the substituent.

When the bond of a substituent is shown as a bond connecting two atoms in a ring, such substituent may be bonded to any ring-forming atom in the substitutable ring.

Those skilled in the art will appreciate that not all nitrogen-containing heterocycles are capable of forming N-oxides since nitrogen requires available lone pairs of electrons to oxidize to oxides; Nitrogen-containing heterocycles. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the use of peroxyacids such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl Hydrogen peroxides such as t-butyl hydroperoxide, sodium perborate and dioxiranes such as dimethyldioxirane are used to oxidize heterocycles and tertiary amines. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see e.g.: T.L. Gilchrist, Comprehensive Organic Synthesis, vol. 7, pp 748-750; A.R. Katritzky and A.J. Boulton, Eds., Academic Press and G.W.H.Cheeseman and E.S.G.Werstiuk, Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A.J. Boulton, Eds., Academic Press.

The present invention also encompasses compounds of the present invention that contain protecting groups. In any process for preparing the compounds of the present invention, it may be necessary and/or desirable to protect sensitive or reactive groups on any relevant molecule, thereby forming chemically protected forms of the compounds of the present invention. This can be accomplished by conventional protecting groups, such as those described in T.W. Greene & P.G.M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1991, which references are incorporated herein by reference. Protecting groups can be removed at an appropriate subsequent stage using methods known in the art.

The term "about" means within ±10% of the stated value, preferably within ±5%, more preferably within ±2%. In this specification, the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond, and * represents the access bond position of the group.

In the present invention, the monocyclic aryl group means that the molecule contains one or at least two phenyl groups. When the molecule contains at least two phenyl groups, the phenyl groups are independent from each other and are connected through a single bond, exemplarily Such as phenyl, biphenyl, terphenyl, etc.; fused-ring aryl refers to the molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but share ring edges and fused with each other, for example Such as naphthyl, anthracenyl, etc.; monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group, when the molecule contains a heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc. ), the heteroaryl group and other groups are independent of each other and are connected through a single bond, such as pyridine, furan, thiophene, etc.; Condensed, or, condensed from at least two heteroaromatic rings, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene and the like.

In the present invention, unless otherwise specified, both the aromatic ring and the heteroaromatic ring include the case of a single ring and a condensed ring.

In the present invention, unless otherwise specified, the substituent is not condensed with the group in which it is located.

The heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S.

In the present invention, the C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, more preferably a C1-C6 chain alkyl group, for example, methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl, etc.

In the present invention, the C3-C20 cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

In the present invention, the substituted or unsubstituted C6-C60 aryl group or C10-C60 fused-ring aryl group is preferably a C6-C30 aryl group, more preferably a C6-C20 aryl group, and preferably the aryl group is composed of a phenyl group , biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl and its derivatives, fluoranthyl, triphenylene, pyrenyl, perylene,

A group in the group consisting of radical and naphthacyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl , p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3- In the group consisting of fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene in the group of ; the pyrene group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthacene is selected from 1-naphthacene, 2-naphthacene In the group formed by the base and 9-naphthacyl.

In the present invention, the substituted or unsubstituted C3-C60 heteroaryl or C3-C60 fused ring heteroaryl is preferably a substituted or unsubstituted C3-C30 heteroaryl or C3-C30 fused ring heteroaryl base, preferably C3-C30 heteroaryl, more preferably C4-C20 heteroaryl, preferably the heteroaryl is furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuran base, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivatives are preferably 9-phenylcarbazole, 9-naphthylcarbazole Benzocarbazole, dibenzocarbazole, or indolocarbazole.

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

The aryloxy group in the present invention includes a monovalent group consisting of the above-mentioned aryl group, heteroaryl group, and oxygen.

The C6-C60 arylamino group mentioned in the present invention includes, for example, phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrylamino, biphenylamino and the like.

The C3-C60 heteroarylamino group mentioned in the present invention includes, for example, a pyridylamino group, a pyrimidinylamino group, a dibenzofuranylamino group, and the like.

In the above substituents, the carbon number of the C1-C10 chain alkyl group can be C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.; the carbon number of the C3-C10 cycloalkyl group can be C4, C5, C6, C7, C8, C9, C10, etc.; the carbon number of the C1-C10 alkoxy group can be C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.; the The carbon number of the C1-C10 thioalkoxy group can be C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.; the carbon number of the C6-C30 monocyclic aryl group can be C10, C12, C14, C16, C18, C20, C26, C28, etc.; the carbon numbers of the C10-C30 fused-ring aryl groups can be C10, C12, C14, C16, C18, C20, C26, C28, etc.; the C3-C30 single The carbon number of the ring heteroaryl group can be C3, C4, C6, C8, C10, C12, C14, C16, C18, C20, C26, C28, etc.; the carbon number of the C6-C30 fused ring heteroaryl group can be C10 , C12, C14, C16, C18, C20, C26, C28, etc.

In the present specification, the C3-C12 cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, preferably a C1-C10 alkyl group and a C3-C10 cycloalkyl group.

Further, in the formula (1), at least one of the ring X and the ring Y is the structure shown in the formula (a), and/or the ring Z is the structure shown in the formula (b):

In formula (a),

represents the position shared with the parent nucleus and connected to the parent nucleus, in formula (b)

represents the position shared with the parent nucleus and connected to the parent nucleus,

Said Z ¹ to Z ⁴ are independently selected from CR ⁷ or N, and said R ⁷ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3 ^- C60 heteroaryl, and the R Rings are connected to form rings or not to form rings;

Said Z ²¹ to Z ²³ are independently selected from CR ⁸ or N, and said R ⁸ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted Or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3- ^C60 heteroaryl, and the R The rings are connected to form a ring or not to form a ring; preferably, at least one R ⁸ in the CR ⁸ is substituted by a group of the structure represented by the formula (G).

Still further, the general formula compound of the present invention has the structure shown in the following formula (1-1):

The definitions of Ar ¹ and Ar ² are the same as those in formula (1);

The definitions of Z ¹ to Z ⁴ are the same as those in formula (a); the definitions of Z ²¹ to Z ²³ are the same as those in formula (b);

Said Z ^1' to Z ^4' are independently selected from CR ¹⁰ or N, and said R ¹⁰ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain Alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino , substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the R ¹⁰ is independently connected to The aromatic rings are connected to form a ring or not to form a ring.

Further, in formula (1), at least one of the Ar ¹ and Ar ² is the structure shown in formula (c):

Said Z ⁵ to Z ⁹ are independently selected from CR ⁹ or N, and said R ⁹ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3- ^C60 heteroaryl, and said R Rings are connected to form rings or not to form rings;

Preferably, in formula (1), between Ar ¹ and the adjacent ring X forms a ring or does not form a ring, and/or between Ar ² and the adjacent ring Y forms a ring or does not form a ring.

Still further, the general formula compound of the present invention has the structure shown in the following formula (1-2) or formula (1-3):

The definition of said Ar ¹ is the same as that in formula (1);

The Z ^2' to Z ^4' are independently selected from CR ¹⁰ or N, and the R ¹⁰ is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chains Alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino , substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the R ¹⁰ is independently connected to The aromatic rings are connected to form a ring or not to form a ring.

Further, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z ²¹ to Z ²³ are independently selected from CR ⁸ or N, and at least one of them is selected from CR ⁸ , and R ⁸ in at least one CR ⁸ is a group of the structure represented by formula (G);

Preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z ²¹ to Z ²³ are each independently selected from CR ⁸ , and R ⁸ in at least one CR ⁸ is a group of the structure represented by formula (G);

Preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z ²¹ to Z ²³ are each independently selected from CR ⁸ , and R ⁸ in at least one CR ⁸ is a group of the structure represented by formula (G), and R ⁸ in the other two CR ⁸ is hydrogen;

More preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z ²² is CR ⁸ , and R ⁸ in the CR ⁸ is of the structure represented by the formula (G). group;

More preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z ²² is CR ⁸ , and R ⁸ in the CR ⁸ is of the structure represented by the formula (G). group, the Z ²¹ and Z ²³ are CR ⁸ , and R ⁸ in the two CR ⁸ is hydrogen at the same time.

Further, the formula (G) of the present invention is the structure shown in any one of the following formula (G-1) to formula (G-6):

Preferably, the structure of formula (G) of the present invention is represented by formula (G-1).

In the formula (1-1), the Z ¹ to Z ⁴ are each independently selected from CR ⁷ or N, and at least one of them is selected from CR ⁷ , and at least one of them is selected from CR ⁷ and R ⁷ is selected from One of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and wherein other R ⁷ in CR ⁷ is selected from hydrogen, substituted or unsubstituted C1- One of C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, the Z ^1' to Z ^4' are independently selected from CR ¹⁰ or N, and at least one of them is selected from CR ¹⁰ , and at least one of them is selected from CR ^10. R ¹⁰ is selected from substituted or unsubstituted One of the C1-C20 chain alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, while the other R ¹⁰ in CR ¹⁰ is selected from hydrogen, substituted or unsubstituted C1-C20 chain alkanes a kind of C3-C20 cycloalkyl group, substituted or unsubstituted;

Preferably, the Z ¹ to Z ⁴ are independently selected from CR ⁷ or N, and at least one of them is selected from CR ⁷ , and at least one of R ⁷ in CR ⁷ is selected from substituted or unsubstituted C1 to One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and wherein other R ⁷ in CR ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, A kind of substituted or unsubstituted C3-C10 cycloalkyl;

And/or, the Z ^1' to Z ^4' are independently selected from CR ¹⁰ or N, and at least one of them is selected from CR ¹⁰ , and at least one of them is selected from CR ^10. R ¹⁰ is selected from substituted or unsubstituted One of the C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while the other R ¹⁰ in CR ¹⁰ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups;

More preferably, the Z ¹ to Z ⁴ are independently selected from CR ⁷ , and Z ³ is selected from CR ⁷ , and R ⁷ in the CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z ¹ -Z ⁴ are selected from CR ⁷ , and R ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z ^1' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^3' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z ¹ to Z ⁴ are each independently selected from CR ⁷ , and wherein Z ³ is selected from CR ⁷ , and R ⁷ in said CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z ¹ -Z ⁴ are selected from CR ⁷ and R ⁷ is selected from hydrogen;

And/or, said Z ^1' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^3' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen;

Still more preferably, the Z ¹ to Z ⁴ are independently selected from CR ⁷ , and Z ² is selected from CR ⁷ , and R ⁷ in the CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z ¹ -Z ⁴ are selected from CR ⁷ , and R ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z ^1' to Z ^4' are each independently selected from CR ¹⁰ , and wherein Z ^2' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z ¹ to Z ⁴ are each independently selected from CR ⁷ , and wherein Z ² is selected from CR ⁷ , and R ⁷ in said CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z ¹ -Z ⁴ are selected from CR ⁷ and R ⁷ is selected from hydrogen;

And/or, said Z ^1' to Z ^4' are each independently selected from CR ¹⁰ , and wherein Z ^2' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z ^4' ^is selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen.

In the formula (1-2), the Z ¹ to Z ⁴ are each independently selected from CR ⁷ or N, and at least one of them is selected from CR ⁷ , and at least one of them is selected from CR ⁷ R ⁷ is selected from One of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and wherein other R ⁷ in CR ⁷ is selected from hydrogen, substituted or unsubstituted C1- One of C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, said Z ^1' to Z ^4' are each independently selected from CR ¹⁰ , and wherein Z ^2' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen;

In formula (1-3), said Z ² to Z ⁴ are independently selected from CR ⁷ or N, and at least one of them is selected from CR ⁷ , and at least one of them is selected from CR ⁷ and R ⁷ is selected from substituted or One of unsubstituted C1-C20 chain alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, and wherein other R ⁷ in CR ⁷ is selected from hydrogen, substituted or unsubstituted C1-C20 chain A kind of alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ or N, and at least one of them is selected from CR ¹⁰ , and at least one of them is selected from CR ¹⁰ , and R ¹⁰ in CR 10 is selected from substituted or unsubstituted One of the C1-C20 chain alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, while the other R ¹⁰ in CR ¹⁰ is selected from hydrogen, substituted or unsubstituted C1-C20 chain alkanes a kind of C3-C20 cycloalkyl group, substituted or unsubstituted;

Preferably, the Z ² to Z ⁴ are independently selected from CR ⁷ or N, and at least one of them is selected from CR ⁷ , and at least one of R ⁷ in CR ⁷ is selected from substituted or unsubstituted C1～ One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and wherein other R ⁷ in CR ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, A kind of substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ or N, and at least one of them is selected from CR ¹⁰ , and at least one of them is selected from CR ¹⁰ , and R ¹⁰ in CR 10 is selected from substituted or unsubstituted One of the C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while the other R ¹⁰ in CR ¹⁰ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups;

More preferably, the Z ² to Z ⁴ are independently selected from CR ⁷ , and Z ³ is selected from CR ⁷ , and R ⁷ in the CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z ¹ -Z ⁴ are selected from CR ⁷ , and R ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^3' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z ² to Z ⁴ are independently selected from CR ⁷ , and wherein Z ³ is selected from CR ⁷ , and R ⁷ in said CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z ¹ -Z ⁴ are selected from CR ⁷ and R ⁷ is selected from hydrogen;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^3' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen;

Still more preferably, said Z ² to Z ⁴ are independently selected from CR ⁷ , and wherein Z ² is selected from CR ⁷ , and R ⁷ in said CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z ¹ -Z ⁴ are selected from CR ⁷ , and R ⁷ is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^2' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z ^4' ^are selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z ² to Z ⁴ are independently selected from CR ⁷ , and wherein Z ² is selected from CR ⁷ , and R ⁷ in said CR ⁷ is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z ¹ -Z ⁴ are selected from CR ⁷ and R ⁷ is selected from hydrogen;

And/or, said Z ^2' to Z ^4' are independently selected from CR ¹⁰ , and wherein Z ^2' is selected from CR ¹⁰ , and R ¹⁰ in said CR ¹⁰ is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z ^4' ^is selected from CR ¹⁰ , and R ¹⁰ is selected from hydrogen.

Still further, in formula (1-1), formula (1-2) or formula (1-3) of the present invention, when R ⁷ and R ¹⁰ are selected from substituted or unsubstituted C1-C20 chain alkanes In the case of one of C3-C20 cycloalkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, R ⁷ and R ¹⁰ are selected from at least one of the following groups:

Preferably, when R ⁷ and R ¹⁰ are selected from substituted or unsubstituted C1-C20 chain alkyl groups and substituted or unsubstituted C3-C20 cycloalkyl groups, R ⁷ and R ¹⁰ are selected from the following groups At least one of:

As the preferred structures of the compounds involved in the present invention, the following specific compounds M1-M150 can be cited, and these compounds are only representative:

As another aspect of the present invention, there is provided an application of the above compound, which is applied to an organic electronic device.

Preferably, the organic electronic devices include organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet type Scanners or electronic paper, most preferably organic electroluminescent devices.

Specifically, the compounds provided by the present invention are preferably used as materials for light-emitting layers in organic electroluminescent devices, more preferably used as materials in light-emitting layers in organic electroluminescent devices, and specifically can be used as materials for light-emitting dye.

As yet another aspect of the present invention, an organic electroluminescent device is also provided, comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first electrode and the second electrode , wherein the light-emitting functional layer contains the compound represented by the general formula (1), formula (1-1), formula (1-2) or formula (1-3) as described above, or contains M as shown above Compounds of structure -1 to M148.

Specifically, an embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, and a first electrode, a plurality of light-emitting functional layers and a second electrode sequentially formed on the substrate; the light-emitting The functional layer includes a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, the hole injection layer is formed on the first electrode layer, and the hole transport layer is formed on the On the hole injection layer, the second electrode layer is formed on the electron transport layer, and a light-emitting layer is formed between the hole transport layer and the electron transport layer; wherein, the light-emitting layer It contains the compound represented by the general formula (1), formula (1-1), formula (1-2) or formula (1-3) as mentioned above, or the compound containing the structure of M-1 to M148 as shown above .

The present invention also discloses a display screen or display panel, in which the organic electroluminescence device as described above is used; preferably, the display screen or display panel is an OLED display.

The present invention also discloses an electronic device, wherein the electronic device has a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescence device as described above.

The OLED device prepared by using the compound of the present invention has low start-up voltage and better service life, and can meet the requirements of current panel manufacturing enterprises for high-performance materials.

The specific reason why the above-mentioned compounds of the present invention are used as light-emitting dyes in the light-emitting layer of organic electroluminescent devices is not clear, but the following reasons are presumed:

1. The boron atom contained in the compound of the present invention has a resonance effect with the nitrogen atom in the same ring, so that this series of materials have the characteristics of narrow spectrum and thermally activated delayed fluorescence emission.

2. In the compounds of the present invention, the substituted aryl group containing N atom is substituted on the aromatic ring directly connected to the central B atom, which can more directly affect the frontier orbital of the molecule. The introduction of such substituted aryl groups containing N atoms can significantly improve the electron transport capacity of the material. Through the adjustment of different substituents, the energy level of the molecule can be adjusted, which can better allow the recombination of carriers in the light-emitting layer, and then It is beneficial to reduce the voltage of the organic electroluminescent device using the compound and improve the life of the device.

In addition, the preparation process of the compound of the present invention is simple and feasible, and the raw materials are readily available, which is suitable for mass production and scale-up.

Detailed ways

The specific preparation methods of the above-mentioned novel compounds of the present invention will be described in detail below by taking multiple synthesis examples as examples, but the preparation methods of the present invention are not limited to these synthesis examples.

It should be noted that obtaining the compound is not limited to the synthetic method and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the compound proposed in the present invention. The compounds of the synthetic methods not mentioned in the present invention are all raw materials obtained through commercial channels, or are self-made according to known methods through these raw materials.

Solvents and reagents used in the present invention, such as chemical reagents such as dichloromethane, petroleum ether, ethanol, tert-butylbenzene, boron tribromide, carbazole, diphenylamine, etc., can be purchased from the domestic chemical product market, such as from Sinopharm Group Reagent Company, TCI Company, Shanghai Bide Pharmaceutical Company, Bailingwei Reagent Company, etc.

The synthesis methods of the compounds of the present invention are briefly described below.

Synthesis Example

Representative synthetic routes are as follows:

The analysis and detection of the intermediates and compounds in the present invention used ABSCIEX mass spectrometer (4000QTRAP).

Synthesis Example 1: Synthesis of M5

Synthesis Example 1

Synthesis of compound M-5:

Preparation of Intermediate M5-1:

Add α-carbazole (29.1g, 173.3mmol, 2.2eq), 1-chloro-2,6-dibromo-4-fluorobenzene (22.4g, 78.7mmol, 1eq), cesium carbonate to a 1L one-neck flask at room temperature (118.1g, 354.1mmol, 4.5eq), N,N-dimethylformamide (500ml), under nitrogen protection, react at 120°C overnight.

Stop heating, add 500 ml of water and stir for 10 min after cooling to room temperature, a large amount of white solid is precipitated, suction filtration, and column chromatography to obtain 30.2 g of white solid.

Synthesis of Intermediate M5-2:

At room temperature, M5-1 (43.4 g, 100 mmol), 3,6-di-tert-butylaniline (90 g, 320 mmol), Pd ₂ (dba) ₃ (2.8 g, 3 mmol), s-Phos (1.2 g, 3 mmol) were mixed ), sodium tert-butoxide (33.6 g, 350 mmol), and xylene (1200 ml) were added to a 2L single-necked flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain 63.1 g of a white solid.

Synthesis of compound M-5:

M5-2 (8.36g, 10mmol) was added to a 500ml there-necked flask, p-tert-butylbenzene (150ml) was added, the reaction system was cooled to -20°C after stirring for 20 minutes, then 15mmol of tert-butyllithium was added to maintain a low temperature Continue stirring for 30 minutes. After that, the temperature was gradually increased to 90 °C, and the heating was continued for 3 h. Finally, the temperature of the reaction system was lowered to -20°C again, boron tribromide (5.1 g, 20 mmol) was added under nitrogen protection, and diisopropylethylamine (13 g, 80 mmol) was added after stirring for 30 minutes. Finally, the reaction system was heated to 110 °C for 12 h. After the reaction had cooled to room temperature, the organic phase was spin-dried under reduced pressure. Ethyl acetate (200 ml) was extracted three times, and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, and 2.9 g of crude product was obtained by column chromatography, and 1.9 g of yellow solid was obtained by recrystallization from toluene/n-hexane, with a purity of 99.37%. Molecular ion mass determined by mass spectrometry: 810.44 (theoretical value: 810.94).

Synthesis Example 2

Synthesis of compound M-15:

Preparation of Intermediate M15-1:

Add γ-carbazole (29.1g, 173.3mmol, 2.2eq), 1-chloro-2,6-dibromo-4-fluorobenzene (22.4g, 78.7mmol, 1eq), cesium carbonate to a 1L single-neck flask at room temperature (118.1g, 354.1mmol, 4.5eq), N,N-dimethylformamide (500ml), under nitrogen protection, react at 120°C overnight.

Synthesis of Intermediate M15-2:

The synthesis scheme is the same as that of M5-2, except that di-tert-butylaniline is replaced by N-(2-methylphenyl)-2-methylaniline, and M5-1 is replaced by M15-1. After column chromatography, 44.7 g white solid.

Synthesis of compound M15:

The synthesis scheme was the same as the synthesis of M5, and M5-2 was replaced by M15-2 (10 mmol) to obtain 1.67 g of a yellow solid with a purity of 99.41%. Molecular ion mass determined by mass spectrometry: 669.14 (theoretical value: 669.27).

Synthesis Example 3

Synthesis of compound M-35:

Preparation of Intermediate M35-1:

Add γ-carbazole (29.1g, 173.3mmol, 2.2eq), 1-chloro-2,6-dibromo-4-fluorobenzene (22.5g, 78.7mmol, 1eq), cesium carbonate to a 1L single-neck flask at room temperature (118.1g, 354.1mmol, 4.5eq), N,N-dimethylformamide (500ml), under nitrogen protection, react at 120°C overnight.

Synthesis of Intermediate M35-2:

At room temperature, M35-1 (43.4g, 100mmol), 3,6-di-tert-butylaniline (45g, 160mmol), Pd2(dba ₎₃ ₍ 1.4g, 1.5mmol), s-Phos (0.6g, 1.5mmol), sodium tert-butoxide (16.8g, 175mmol), and xylene (800ml) were added to a 2L single-neck flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain 42.3 g of white solids.

Synthesis of Intermediate M35-3:

At room temperature, M35-2 (31.7g, 50mmol), 4,4'-bis(phenylisopropyl)diphenylamine (32.2g, 80mmol), Pd2(dba ₎₃ ₍ 0.7g, 0.75mmol), s-Phos (0.3 g, 0.75 mmol), sodium tert-butoxide (12 g, 100 mmol), and xylene (600 ml) were added to a 1 L single-neck flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain 26.2 g of white solid.

Synthesis of compound M35:

The synthesis scheme was the same as that of M5, and M5-2 was replaced by M35-3 (10 mmol) to obtain 1.79 g of a yellow solid with a purity of 99.71%. Molecular ion mass determined by mass spectrometry: 935.14 (theoretical value: 935.07).

Synthesis Example 4

Synthesis of Compound M-94

Preparation of Intermediate M94-1:

Add α-phenothiazine (31.8g, 173.3mmol, 2.2eq), 1-chloro-2,6-dibromo-4-fluorobenzene (22.4g, 78.7mmol, 1eq), carbonic acid to a 1L one-neck flask at room temperature Cesium (118.1g, 354.1mmol, 4.5eq), N,N-dimethylformamide (600ml), under nitrogen protection, react at 120°C overnight.

Stop heating, add 600 ml of water and stir for 10 min after cooling to room temperature, a large amount of white solid is precipitated, suction filtration, and column chromatography to obtain 26.2 g of white solid.

Synthesis of Intermediate M94-2:

The synthesis scheme is the same as the synthesis of M5-2, M5-1 is replaced by M94-1, and di-tert-butylaniline is replaced by di-tert-butylcarbazole, and 51.2 g of white solid is obtained after column chromatography.

Synthesis of compound M94:

The synthesis scheme was the same as the synthesis of M5, and M5-2 was replaced by M94-2 (10 mmol) to obtain 2.23 g of a yellow solid with a purity of 99.47%. Molecular ion mass determined by mass spectrometry: 882.17 (theoretical value: 822.90).

The following representative specific compounds of the present invention are prepared with reference to the above-mentioned synthetic scheme, and the mass spectrometry theoretical value and test data value of each compound are shown in the following table 1.

Table 1:

化合物编号Compound number	质谱理论值Theoretical value of mass spectrometry	质谱测试数据Mass Spectrometry Test Data
M-8M-8	810.48810.48	810.72810.72
M-18M-18	754.42754.42	754.66754.66
M-25M-25	1058.541058.54	1058.781058.78
M-30M-30	934.51934.51	934.69934.69
M-41M-41	914.54914.54	914.71914.71

M-57M-57	806.45806.45	806.66806.66
M-65M-65	587.22587.22	587.36587.36
M-68M-68	587.22587.22	587.29587.29
M-85M-85	680.31680.31	680.48680.48
M-93M-93	826.47826.47	826.49826.49
M-149M-149	698.35698.35	698.39698.39
M-150M-150	698.35698.35	698.47698.47

Device Embodiment

Implementation

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

In particular embodiments, a substrate may be used under the first electrode or over the second electrode. The substrates are glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. In addition, a thin film transistor (TFT) may be provided on a substrate as a display.

The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In) can be used ), magnesium-silver (Mg-Ag) and other metals or alloys, and any combination between them.

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

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

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

The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of the above-mentioned HT-1 to HT-51, or use one or more compounds of the following HI-1-HI-3; HT-1 can also be used One or more compounds to HT-51 are doped with one or more of the following HI-1-HI-3 compounds.

The light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue. The monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other. The light-emitting layer may also be a single-color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.

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

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

In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer can use, but is not limited to, one or more compounds of the above-mentioned HT-1 to HT-51, or use, but not limited to, one or more compounds of the following PH-47 to PH-77; or Mixtures of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 are employed, but not limited to.

The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be an electron transport layer (ETL) with a single-layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, a combination of one or more of ET-1 to ET-65 listed below.

In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds of the above-mentioned ET-1 to ET-65, or adopt, but not limited to, one or more compounds of the following PH-1 to PH-46; Mixtures of one or more compounds of ET-1 to ET-65 and one or more of PH-1 to PH-46 may also be employed, but are not limited to.

The device can also include an electron injection layer between the electron transport layer and the cathode, and the material of the electron injection layer includes but is not limited to one or more combinations listed below:

LiQ, LiF, _NaCl , CsF, _Li2O , _Cs2CO3 , BaO, Na, Li, Ca, Mg, Yb.

Device Example 1:

The preparation process of the organic electroluminescent device in this embodiment is as follows:

The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in an acetone:ethanol mixed solvent, baked in a clean environment until the water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;

The above-mentioned glass substrate with anode was placed in a vacuum chamber, evacuated to <1 × 10 ^-5 Pa, and 10nm of HT-4:HI-3 (97 nm) was vacuum thermally evaporated on the above-mentioned anode layer film in sequence. /3,w/w) mixture as hole injection layer, 60nm compound HT-4 as hole transport layer, 5nm compound HT-14 as electron blocking layer; 20nm compound BFH-4:M-5(100: 3,w/w) binary mixture as light-emitting layer; 5nm of ET-23 as hole blocking layer, 25nm of compound ET-61:ET-57 (50/50,w/w) mixture as electron transport layer, 1nm of LiF as the electron injection layer and 150nm metal aluminum as the cathode. The total evaporation rate of all organic layers and LiF was controlled at 0.1 nm/sec, and the evaporation rate of metal electrodes was controlled at 1 nm/sec.

Device Example 2 to Device Example 10 are produced by the same method as in Device Example 1, except that the luminescent dyes in the luminescent layer are replaced by compounds M-5 of the present invention with compounds M-8, M-18, M- 25, M-30, M-41, M-57, M-65, M-85, M-137.

Device Comparative Example 1 to Device Comparative Example 3 were fabricated by the same method as in Device Example 1, except that the luminescent dyes in the luminescent layer were replaced by the compounds M-5 of the present invention with compounds Ref-1, Ref-2 and Ref-2 in the prior art, respectively. Ref-3.

Device test method:

The following performance measurements were performed on the organic electroluminescent devices prepared by the above process:

Under the same brightness, a digital source meter and PR650 were used to measure the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1 to 13 and Comparative Examples 1 to 3, as well as the device life. Specifically, the voltage is increased at a rate of 0.1V per ^second , and the voltage when the brightness of the organic electroluminescent device reaches 1000cd/m2 is determined as the driving voltage at the corresponding brightness. At the same time, the device can be directly tested on PR650. External quantum efficiency (EQE%);

The life test of LT95 is as follows: using a luminance meter at a luminance of 1000cd/ ^m2 , maintaining a constant current, measure the time for the luminance of the organic electroluminescent device to drop to 950cd/ ^m2 , in hours.

The properties of the organic electroluminescent devices prepared in each of the above device embodiments and comparative examples are shown in Table 2 below.

Table 2:

All devices emit blue light; in addition, the full width half maximum of the emission spectrum is less than 40 nm, which is characterized by a narrow spectrum.

As can be seen from Table 2, under the condition that the material schemes and preparation processes of other functional layers in the organic electroluminescence device structure are completely the same, the organic electroluminescence devices prepared by the device examples 1-13 of the present invention are compared with the comparative examples. The organic electroluminescence device prepared in 1-3 can effectively reduce the take-off and drop voltage of the device and improve the current efficiency of the device. The above experimental data show that the novel organic material of the present invention, as a light-emitting layer material of an organic electroluminescent device, is a blue-light material with good performance and has broad application prospects.

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

Claims

A compound whose structure is shown in general formula (1):

In formula (1):

The ring X, ring Y and ring Z are each independently selected from one of substituted or unsubstituted C5-C30 aromatic rings and substituted or unsubstituted C3-C30 heteroaromatic rings; further, the ring X , Ring Y and Ring Z are each independently selected from a substituted or unsubstituted C5-C14 aromatic ring, a substituted or unsubstituted C3-C14 heteroaromatic ring; further, the ring X, ring Y and Ring Z is independently selected from a substituted or unsubstituted C5-C8 aromatic ring, a substituted or unsubstituted C5-C8 heteroaromatic ring;

The Ar 1 and Ar 2 are each independently selected from a substituted or unsubstituted C6-C60 aryl group and a substituted or unsubstituted C3-C60 heteroaryl group;

Ar 1 forms a ring or does not form a ring between the adjacent ring X or ring Z, and between Ar 2 and the adjacent ring Y or ring Z forms a ring or does not form a ring;

And at least one of the ring X, ring Y, ring Z, Ar 1 and Ar 2 is substituted by a group of the structure represented by formula (G);

Preferably, one of the ring X, ring Y, ring Z, Ar 1 and Ar 2 is substituted by a group of the structure represented by the formula (G); more preferably, the ring Z is replaced by a group of the structure represented by the formula (G) replaced by the regiment;

In formula (G):

Said X 1 to X 8 are each independently selected from CR 1 or N, and said R 1 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted Or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3 - C60 heteroaryl, and the R Rings are connected into rings or not connected into rings, and at least one of X 1 -X 8 is N;

The n is 0 or 1, and E 1 is selected from one of CR 2 R 3 , NR 4 , O, S, SiR 5 R 6 ;

The R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 cycloalkyl One of unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

When the above groups have substituents, the substituents are selected from halogen, cyano, carbonyl, nitro, amino, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl group, C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 monocyclic aryl group or fused-ring aryl group, C3-C60 monocyclic heteroaryl group or fused-ring heteroaryl group one or a combination of at least two.
The compound of claim 1, wherein each of Ring X, Ring Y and Ring Z is independently selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzene ring, a substituted or unsubstituted thiophene ring, a One of unsubstituted naphthalene ring, substituted or unsubstituted phenanthrene ring or substituted or unsubstituted carbazole ring.
The compound according to claim 1 or 2, in the formula (1), at least one of the ring X and the ring Y is the structure represented by the formula (a), and/or the ring Z is the formula (b) Structure shown:

Said Z 1 to Z 4 are independently selected from CR 7 or N, and said R 7 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3 - C60 heteroaryl, and the R Rings are connected to form rings or not to form rings;

Said Z 21 to Z 23 are independently selected from CR 8 or N, and said R 8 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted Or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3- C60 heteroaryl, and the R The ring is connected to form a ring or not connected to form a ring; preferably at least one R 8 in the CR 8 is substituted by a group of the structure represented by the formula (G),

In formula (a),
represents the position shared with the parent nucleus and connected to the parent nucleus, in formula (b)
Represents a position shared with the parent nucleus and attached to the parent nucleus.
The compound according to claim 3, wherein the compound has a structure represented by the following formula (1-1):

The definitions of Ar 1 and Ar 2 are the same as those in formula (1);

The definitions of Z 1 to Z 4 are the same as those in formula (a); the definitions of Z 21 to Z 23 are the same as those in formula (b);

Said Z 1' to Z 4' are independently selected from CR 10 or N, and said R 10 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain Alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino , substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the R 10 is independently connected to The aromatic rings are connected to form a ring or not to form a ring.
The compound according to any one of claims 1 to 4, in formula (1), at least one of Ar 1 and Ar 2 is a structure represented by formula (c):

Said Z 5 to Z 9 are independently selected from CR 9 or N, and said R 9 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkane base, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted Or one of unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3- C60 heteroaryl, and said R Rings are connected to form rings or not to form rings;

Preferably, in formula (1), between Ar 1 and the adjacent ring X forms a ring or does not form a ring, and/or between Ar 2 and the adjacent ring Y forms a ring or does not form a ring.
The compound according to claim 5, wherein the compound has a structure represented by the following formula (1-2) or formula (1-3):

The definition of said Ar 1 is the same as that in formula (1);

The Z 2' to Z 4' are independently selected from CR 10 or N, and the R 10 is independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chains Alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino , substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, the R 10 is independently connected to The aromatic rings are connected to form a ring or not to form a ring.
The compound according to claim 4 or 6, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z 21 to Z 23 are independently selected from CR 8 or N, and at least one of them is selected from CR 8 , and R 8 in at least one of CR 8 is a group of the structure represented by formula (G);

Preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z 21 to Z 23 are each independently selected from CR 8 , and R 8 in at least one CR 8 is a group of the structure represented by formula (G);

Preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z 21 to Z 23 are each independently selected from CR 8 , and R 8 in at least one CR 8 is a group of the structure represented by formula (G), and R 8 in the other two CR 8 is hydrogen;

More preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z 22 is CR 8 , and R 8 in the CR 8 is of the structure represented by the formula (G). group;

More preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), the Z 22 is CR 8 , and R 8 in the CR 8 is of the structure represented by the formula (G). group, the Z 21 and Z 23 are CR 8 , and R 8 in the two CR 8 is hydrogen at the same time.
The compound according to claim 1 or 7, wherein the formula (G) is a structure represented by any one of the following formulae (G-1) to (G-6):

The structure of the formula (G) is preferably represented by the formula (G-1).
The compound according to claim 4, in the formula (1-1), the Z 1 to Z 4 are each independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of them is selected from R 7 in CR 7 is selected from one of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, while the other R 7 in CR 7 is selected from One of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, the Z 1' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10. R 10 is selected from substituted or unsubstituted One of the C1-C20 chain alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C20 chain alkanes a kind of C3-C20 cycloalkyl group, substituted or unsubstituted;

Preferably, the Z 1 to Z 4 are independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of them is selected from CR 7. R 7 is selected from substituted or unsubstituted C1 to One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and wherein other R 7 in CR 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, A kind of substituted or unsubstituted C3-C10 cycloalkyl;

And/or, the Z 1' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10. R 10 is selected from substituted or unsubstituted One of the C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups;

More preferably, the Z 1 to Z 4 are independently selected from CR 7 , and Z 3 is selected from CR 7 , and R 7 in the CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z 1 -Z 4 are selected from CR 7 , and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 1' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 1 to Z 4 are each independently selected from CR 7 , and wherein Z 3 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z 1 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen;

And/or, said Z 1' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen;

Still more preferably, the Z 1 to Z 4 are independently selected from CR 7 , and Z 2 is selected from CR 7 , and R 7 in the CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z 1 -Z 4 are selected from CR 7 , and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 1' to Z 4' are each independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 1 to Z 4 are each independently selected from CR 7 , and wherein Z 2 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z 1 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen;

And/or, said Z 1' to Z 4' are each independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z 4' is selected from CR 10 , and R 10 is selected from hydrogen.
The compound according to claim 6, in the formula (1-2), the Z 1 to Z 4 are each independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of them is selected from R 7 in CR 7 is selected from one of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, while the other R 7 in CR 7 is selected from One of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10 , and R 10 in CR 10 is selected from substituted or unsubstituted One of the C1-C20 chain alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C20 chain alkanes a kind of C3-C20 cycloalkyl group, substituted or unsubstituted;

Preferably, the Z 1 to Z 4 are independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of them is selected from CR 7. R 7 is selected from substituted or unsubstituted C1 to One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and wherein other R 7 in CR 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, A kind of substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10 , and R 10 in CR 10 is selected from substituted or unsubstituted One of the C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups;

More preferably, the Z 1 to Z 4 are independently selected from CR 7 , and Z 3 is selected from CR 7 , and R 7 in the CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z 1 -Z 4 are selected from CR 7 , and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 1 to Z 4 are each independently selected from CR 7 , and wherein Z 3 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z 1 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen;

Still more preferably, the Z 1 to Z 4 are independently selected from CR 7 , and Z 2 is selected from CR 7 , and R 7 in the CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other Z 1 -Z 4 are selected from CR 7 , and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 1 to Z 4 are each independently selected from CR 7 , and wherein Z 2 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and other R 7 in Z 1 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 1'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen;

In formula (1-3), said Z 2 to Z 4 are independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of them is selected from CR 7 and R 7 is selected from substituted or One of unsubstituted C1-C20 chain alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, and wherein other R 7 in CR 7 is selected from hydrogen, substituted or unsubstituted C1-C20 chain A kind of alkyl, substituted or unsubstituted C3-C20 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10 , and R 10 in CR 10 is selected from substituted or unsubstituted One of the C1-C20 chain alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C20 chain alkanes a kind of C3-C20 cycloalkyl group, substituted or unsubstituted;

Preferably, the Z 2 to Z 4 are independently selected from CR 7 or N, and at least one of them is selected from CR 7 , and at least one of R 7 in CR 7 is selected from substituted or unsubstituted C1～ One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and wherein other R 7 in CR 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, A kind of substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 or N, and at least one of them is selected from CR 10 , and at least one of them is selected from CR 10 , and R 10 in CR 10 is selected from substituted or unsubstituted One of the C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while the other R 10 in CR 10 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkanes one of cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups;

More preferably, the Z 2 to Z 4 are independently selected from CR 7 , and Z 3 is selected from CR 7 , and R 7 in the CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while other Z 2 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 2'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 2 to Z 4 are independently selected from CR 7 , and wherein Z 3 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and the other R7 in Z2 - Z4 is selected from CR7, and R7 is selected from hydrogen;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 3' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 2'-Z 4' is selected from CR 10 , and R 10 is selected from hydrogen;

Still more preferably, said Z 2 to Z 4 are independently selected from CR 7 , and wherein Z 2 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, while other Z 2 -Z 4 are selected from CR 7 and R 7 is selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups , a substituted or unsubstituted C3-C10 cycloalkyl;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 2'-Z 4' are selected from CR 10 , and R 10 is selected from hydrogen, substituted or unsubstituted C1- One of C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

More preferably, said Z 2 to Z 4 are independently selected from CR 7 , and wherein Z 2 is selected from CR 7 , and R 7 in said CR 7 is selected from substituted or unsubstituted C1-C10 chain alkanes one of C3-C10 cycloalkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, and the other R7 in Z2 - Z4 is selected from CR7, and R7 is selected from hydrogen;

And/or, said Z 2' to Z 4' are independently selected from CR 10 , and wherein Z 2' is selected from CR 10 , and R 10 in said CR 10 is selected from substituted or unsubstituted C1 to C10 One of chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, while other R 10 in Z 2'-Z 4' is selected from CR 10 , and R 10 is selected from hydrogen.
The compound according to claim 9 or 10, in formula (1-1), formula (1-2) or formula (1-3), when R 7 and R 10 are selected from substituted or unsubstituted C1~ When one of C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, R 7 and R 10 are selected from at least one of the following groups:

Preferably, when R 7 and R 10 are selected from substituted or unsubstituted C1-C20 chain alkyl groups and substituted or unsubstituted C3-C20 cycloalkyl groups, R 7 and R 10 are selected from the following groups At least one of:
The compound according to claim 1, which has the structure shown below:
An application of the compound according to any one of claims 1-12, the application is as a functional material in an organic electronic device, the organic electronic device includes an organic electroluminescence device, an optical sensor, a solar cell, Lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet-type scanners or electronic paper;

Preferably, the application of the compound is as a light-emitting layer material in organic electroluminescent devices, in particular as a light-emitting layer light-emitting dye.
An organic electroluminescence device, comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layer contains claims The compound described in any one of 1-12;

Preferably, the light-emitting functional layer includes a hole transport region, a light-emitting layer, and an electron transport region, the hole transport region is formed on the anode layer, and the cathode layer is formed on the electron transport region , between the hole transport region and the electron transport region is a light-emitting layer; wherein, the light-emitting layer contains the compound according to any one of claims 1-12.