CN114478594A

CN114478594A - Novel boron-containing organic compound and application thereof

Info

Publication number: CN114478594A
Application number: CN202011162123.7A
Authority: CN
Inventors: 李国孟; 李熠烺; 孙磊; 徐超; 曾礼昌
Original assignee: Beijing Eternal Material Technology Co Ltd
Current assignee: Beijing Eternal Material Technology Co Ltd
Priority date: 2020-10-27
Filing date: 2020-10-27
Publication date: 2022-05-13
Also published as: WO2022089415A1

Abstract

The invention relates to a compound and application thereof, wherein the compound has a structure shown in a formula (1). The compound provided by the invention introduces a substituted aryl group containing N atoms into a B-N resonance type material, and the substituted aryl group containing N atoms is substituted on an aromatic ring directly connected with a central B atom and the N atom. When the compound is used as an organic electroluminescent device, particularly as a luminescent layer material, the carrier transmission balance in the device can be effectively improved, so that the excellent effects of high luminous efficiency and low starting voltage of the device are ensured.

Description

Novel boron-containing organic compound and application thereof

Technical Field

The invention relates to a boron-containing organic material, belongs to the technical field of organic luminescent materials, and also relates to application of the compound in an organic electroluminescent device.

Background

The main way people acquire information is through vision, so that a display device is of great importance in the process of human interaction with information. Organic electroluminescent diodes (OLEDs) have many advantages such as flexibility, self-luminescence, high contrast, large size, and low power consumption, and are one of the mainstream display devices at present.

Among them, the red and green dyes as three primary colors generally contain heavy atoms such as Ir, Pt, etc., theoretically can achieve 100% internal quantum efficiency, have high electroluminescent efficiency and low power consumption, and become the mainstream of the current commercial display devices. However, the chromaticity and lifetime of blue phosphorescent materials are not sufficient for current commercial display. Currently, blue devices still use traditional fluorescent materials to achieve high color purity and long device lifetime.

Recently, researchers of Takuji Hatakeyyama and Junji Kido in Japan reported a series of DABNA-1(Adv. Mater.2016,28, 2777-. Compared with the traditional blue fluorescent dye, the compound has narrower spectrum and high color purity. However, the rigid planar structure also causes the difference between the singlet state and the triplet state energy level to be large, the reverse system crossing from the triplet state to the singlet state is slow, excitons can cause serious efficiency roll-off after being compounded on the dye, and the service life of the device is short. In addition, a rigid structure that is too planar also tends to cause adverse effects such as spectral broadening and red-shift due to too high a doping concentration.

Konika minolta (WO2019163625A) discloses a boron-containing organic material, wherein the boron-containing organic material is combined with a fluorine-containing solvent component and used as an electron transport material, compounds containing N atoms for substituting aryl are B-O coordination materials, and if the B-O coordination materials are connected with the compounds containing N atoms for substituting aryl, the resonance characteristics of the B-O coordination materials are easily broken, so that a D-A type material is formed, the D-A type material has a stronger CT state, and the luminescence spectrum is widened, thus the characteristic of the narrow spectrum of the boron-containing organic material is lost. Cenicrocarneda (CN109155370A) also discloses a class of boron-containing organic materials that require a central B atom to be coordinated with 3 surrounding atoms, one of which must be N, the remaining 2 of which may be O or S.

The existing organic electroluminescent materials still have a lot of room for improvement in light emitting performance, and there is a need to develop a new light emitting material system to meet the commercialization demand.

Disclosure of Invention

In order to solve the technical problems, the invention provides a compound containing a novel structure and a general formula B, wherein a substituted aryl group containing N atoms is introduced into a B-N resonance type material, and is substituted on an aromatic ring directly connected with a central B atom and the central N atom, the B-N coordination material has strong self-stability, and can still maintain the self-narrow spectrum emission characteristic after being connected with the substituted aryl group containing the N atoms.

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

in formula (1):

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

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

Ar¹And Ar²Each independently selected from one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

Ar¹with or without rings, Ar, between adjacent rings X or Z²Form a ring or not form a ring with the adjacent ring Y or the ring Z; and said ring X, ring Y, ring Z, Ar¹And Ar²Is substituted with a group of the structure represented by formula (G);

preferably, said ring X, ring Y, ring Z, Ar¹And Ar²Is substituted with a group of the structure represented by formula (G); more preferably, the ring Z is substituted with a group of the structure represented by formula (G);

in the formula (G):

X₁-X₈each independently selected from CR¹Or N, said R¹Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl¹Independently linked to the linking aromatic ring to form a ring or not, and X₁-X₈Is N;

n is 0 or 1, E¹Selected from the group consisting of CR²R³、NR⁴、O、S、SiR⁵R⁶One of (1);

when n is 0, it represents E¹In the absence, when in formula (G) and E¹The two atoms connected are directly connected by a single bond;

R²、R³、R⁴、R⁵and R⁶Each independently selected from one of hydrogen, 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 aryl and substituted or unsubstituted C3-C60 heteroaryl;

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

In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.

In the present specification, the expression of Ca to Cb represents that the group has a carbon number of a to b, and generally the carbon number does not include the carbon number of the substituent unless otherwise specified.

In the present specification, the expression "-" of the underlined loop structure means that the linking site is located at any position on the loop structure where a bond can be formed, and denotes the position of the bonding site of the group.

In the present invention, the monocyclic aryl group means that one or at least two phenyl groups are contained in a molecule, and when the at least two phenyl groups are contained in a molecule, the phenyl groups are independent of each other and are connected by a single bond, such as phenyl, biphenylyl, terphenylyl, and the like, for example; the fused ring aryl group means that at least two benzene rings are contained in the molecule, but the benzene rings are not independent of each other, but common ring sides are fused with each other, and exemplified by naphthyl, anthryl and the like; monocyclic heteroaryl refers to a compound having at least one heteroaryl group in the molecule, and when a heteroaryl group and other groups (e.g., aryl, heteroaryl, alkyl, etc.) are present in the molecule, the heteroaryl and other groups are independently linked by a single bond, illustratively pyridine, furan, thiophene, etc.; fused ring heteroaryl refers to a fused ring of at least one phenyl group and at least one heteroaryl group, or, fused ring of at least two heteroaryl rings, illustratively quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, and the like.

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

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

The hetero atom in the present invention generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably N, O, S.

The atomic names given in this disclosure, including their respective isotopes, for example, hydrogen (H) includes¹H (protium or H),²H (deuterium or D), etc.; carbon (C) then comprises¹²C、¹³C and the like.

In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, and the like.

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, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl and the like.

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

In the present invention, the substituted or unsubstituted C6-C60 aryl group or C10-C60 condensed ring aryl group is preferably C6-C30 aryl group, more preferably C6-C20 aryl group, and preferably the aryl group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group and derivatives thereof, anthryl group, triphenylene group, pyrenyl group, perylenyl group, perylene group, or the like,

Radicals of the group consisting of radicals and tetracenyl radicals. The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from the group consisting of 1-anthracene group, 2-anthracene group, and 9-anthracene group; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9 '-dimethylfluorene, 9' -spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracene group is selected from the group consisting of 1-tetracene, 2-tetracene, and 9-tetracene.

In the present invention, the substituted or unsubstituted C3-C60 heteroaryl or C3-C60 fused ring heteroaryl is preferably substituted or unsubstituted C3-C30 heteroaryl or C3-C30 fused ring heteroaryl, preferably C3-C30 heteroaryl, and more preferably C4-C20 heteroaryl, and preferably the heteroaryl is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl, or a derivative thereof, wherein the carbazolyl derivative is 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 above-mentioned examples of the aryl group. Specific examples of the heteroarylene group in the present invention include divalent groups obtained by removing one hydrogen atom from the above-mentioned examples of the heteroaryl group.

Examples of the aryloxy group in the present invention include monovalent groups composed of the above aryl group, heteroaryl group and oxygen.

Examples of the C6-C60 arylamino group in the present invention include: phenylamino, methylphenylamino, naphthylamino, anthrylamino, phenanthrylamino, biphenylamino and the like.

Examples of the heteroarylamino group having C3 to C60 in the present invention include: pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.

Among the above substituents, the carbon number of the chain alkyl group having from C1 to C10 may be C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.; the carbon number of the C3-C10 cycloalkyl can be C4, C5, C6, C7, C8, C9, C10 and the like; the C1-C10 alkoxy group may have C2, C3, C4, C5, C6, C7, C8, C9, C10, or the like; the C1-C10 thioalkoxy group may have C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.; the C6-C30 monocyclic aryl group may have C10, C12, C14, C16, C18, C20, C26, C28, etc.; the number of carbons of the C10-C30 condensed ring aryl group may be C10, C12, C14, C16, C18, C20, C26, C28, etc.; the monocyclic heteroaryl group having carbon atoms of C3-C30 may 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 may be C10, C12, C14, C16, C18, C20, C26, C28 and the like.

In the present specification, the C3-C12 cycloalkyl group includes monocycloalkyl and polycycloalkyl groups, preferably C1-C10 alkyl and C3-C10 cycloalkyl groups.

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

z is¹～Z⁴Are each independently selected from CR⁷Or N, said R⁷Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl⁷Independently with the attached aromatic ring to form a ring or not;

z is²¹～Z²³Are each independently selected from CR⁸Or N, said R⁸Independently selected from one of 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 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C60 heteroaryl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, and R is a substituent selected from the group⁸Independently with the attached aromatic ring to form a ring or not; preferably the CR⁸At least one R of⁸Substituted with a group of the structure represented by formula (G).

Still further, the compound of the general formula of the present invention has a structure represented by the following formula (1-1):

ar is¹、Ar²Is the same as defined in formula (1);

Z¹～Z⁴is as defined in formula (a); z²¹～Z²³Is as defined in formula (b);

z is^1’～Z^4’Are each independently selected from CR¹⁰Or N, said R¹⁰Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl¹⁰Independently with or without the attached aromatic ring.

Further, in the formula (1), Ar is¹And Ar²At least one of (a) is represented by the formula (c)The structure shown is as follows:

z is⁵～Z⁹Are each independently selected from CR⁹Or N, said R⁹Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl⁹Independently with the attached aromatic ring to form a ring or not;

preferably, in the formula (1), Ar¹With or without rings formed between adjacent rings X, and/or Ar²And the adjacent rings Y are provided with or without rings.

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

ar is¹Is the same as defined in formula (1);

z is^2’～Z^4’Are each independently selected from CR¹⁰Or N, said R¹⁰Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl¹⁰Independently linked to the aromatic ring to which they are attached to form a ring or notAre connected into a ring.

Further, in the above formula (1-1), formula (1-2) or formula (1-3), Z²¹～Z²³Are each independently selected from CR⁸Or N, and wherein at least one is selected from CR⁸And wherein at least one CR is⁸R in (1)⁸A group having a structure represented by formula (G);

preferably, in said formula (1-1), formula (1-2) or formula (1-3), said Z²¹～Z²³Are each independently selected from CR⁸And wherein at least one CR is⁸R in (1)⁸A group having a structure represented by formula (G);

preferably, in said formula (1-1), formula (1-2) or formula (1-3), said Z²¹～Z²³Are each independently selected from CR⁸And wherein at least one CR is⁸R in (1)⁸Is a group of the structure of formula (G) with the other two CR's therein⁸R in (1)⁸Is hydrogen;

more preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), Z²²Is CR⁸The CR of⁸R in (1)⁸A group having a structure represented by formula (G);

more preferably, in the formula (1-1), the formula (1-2) or the formula (1-3), Z²²Is CR⁸The CR of⁸R in (1)⁸A group of the structure of formula (G), said Z²¹And Z²³Is CR⁸The two CR⁸R in (1)⁸And is also hydrogen.

Further, the formula (G) of the present invention has a structure represented by any one of the following formulae (G-1) to (G-6):

preferably, the formula (G) of the present invention has a structure represented by the formula (G-1).

In the formula (1-1), Z¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷Is selected from the group consisting ofOne of substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰Or N, and wherein at least one is selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

preferably, Z is¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰Or N, and wherein at least one is selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷Selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3 to C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstitutedOne of substituted C3-C10 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the others are selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen.

In the formula (1-2), Z¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰Or N, and whereinAt least one selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

preferably, Z is¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰What is, what isThe CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen;

in the formula (1-3), the Z²～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰Or N, and wherein at least one is selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

it is preferable thatZ is the same as²～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰Or N, and wherein at least one is selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen;

still more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷Selected from substituted or unsubstitutedC1-C10 chain alkyl, substituted or unsubstituted C3-C10 naphthenic base, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen.

Still further, in the formula (1-1), the formula (1-2) or the formula (1-3) of the present invention, when R is mentioned⁷And R¹⁰When one is selected from the group consisting of substituted or unsubstituted C1-C20 chain alkyl groups and substituted or unsubstituted C3-C20 cycloalkyl groups, R⁷And R¹⁰At least one selected from the following groups:

preferably R⁷And R¹⁰When one is selected from the group consisting of substituted or unsubstituted C1-C20 chain alkyl groups and substituted or unsubstituted C3-C20 cycloalkyl groups, R⁷And R¹⁰At least one selected from the following groups:

preferred structures of the compounds according to the present invention include the following specific compounds M1-M150, which are representative:

as another aspect of the present invention, there is provided a use of the above compound for an organic electronic device.

Preferably, the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner, or electronic paper, most preferably an organic electroluminescent device.

Specifically, the compound provided by the invention is preferably applied as a material of a light-emitting layer in an organic electroluminescent device, more preferably applied as a material in the light-emitting layer in the organic electroluminescent device, and particularly can be applied as a light-emitting dye.

As still another aspect of the present invention, there is also provided an organic electroluminescent 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 a compound represented by general formula (1), formula (1-2), or formula (1-3) as described above, or a compound having a structure of M-1 to M148 as described above.

Specifically, one embodiment of the present invention provides an organic electroluminescent device including 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 functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the first electrode layer, the hole transport layer is formed on the hole injection layer, the second electrode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; wherein the light-emitting layer contains a compound represented by the general formula (1), the formula (1-2) or the formula (1-3) or a compound represented by the structures from M-1 to M148.

The invention also discloses a display screen or a display panel, wherein the display screen or the display panel adopts the organic electroluminescent device; preferably, the display screen or the display panel is an OLED display.

The invention also discloses electronic equipment, wherein the electronic equipment is provided with a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescent device.

The OLED device prepared by the compound has low starting voltage and better service life, and can meet the requirements of panel manufacturing enterprises on high-performance materials at present.

The specific reason why the above-mentioned compound of the present invention is excellent as a light-emitting dye in a light-emitting layer in an organic electroluminescent device is not clear, and the following reason is presumed to be possible:

1. the boron atom contained in the compound has resonance effect with the nitrogen atom in the same ring, so that the series of materials have the characteristics of narrow spectrum and thermal activation delayed fluorescence emission.

2. In the compounds of the present invention, the substituted aryl group containing an N atom may have a more direct effect on the front orbital of the molecule by substituting it on the aromatic ring directly connected to the central B atom. The introduction of the substituted aryl containing N atoms can obviously improve the electron transmission capability of the material, and the energy level of molecules can be adjusted by adjusting different substituents, so that the current carriers can be better compounded in a light-emitting layer, and the voltage reduction and the service life improvement of an organic electroluminescent device adopting the compound are facilitated.

In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.

Detailed Description

The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.

It should be noted that the method and materials for obtaining the compound are not limited to the synthetic methods and materials used in the present invention, and those skilled in the art may 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 starting products obtained commercially or are self-made by these starting products according to known methods.

The solvents and reagents used in the present invention, such as methylene chloride, petroleum ether, ethanol, tert-butyl benzene, boron tribromide, carbazole, diphenylamine, and other chemical reagents, can be purchased from domestic chemical product markets, such as from national drug group reagent, TCI, shanghai bibi medicine, welfare agent, and the like.

The synthesis of the compounds of the present invention is briefly described below.

Synthetic examples

A representative synthetic route is as follows:

analytical testing of intermediates and compounds in the present invention uses an abciex mass spectrometer (4000 QTRAP).

Synthesis example 1: synthesis of M5

Synthesis example 1

Synthesis of Compound M-5:

preparation of intermediate M5-1:

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

Stopping heating, cooling to room temperature, adding 500ml water, stirring for 10min, precipitating a large amount of white solid, vacuum filtering, and performing column chromatography to obtain 30.2g of white solid.

Synthesis of intermediate M5-2:

m5-1(43.4g, 100mmol), 3, 6-di-tert-butylaniline (90g, 320mmol), Pd was added at room temperature₂(dba)₃(2.8g, 3mmol), s-Phos (1.2g, 3mmol), sodium t-butoxide (33.6g, 350mmol), xylene (1200ml) were added to a 2L single-neck flask, replaced with nitrogen three times, and heated to 130 ℃ for reaction 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 63.1g of a white solid.

Synthesis of Compound M-5:

m5-2(8.36g, 10mmol) was added to a 500ml three-necked flask, p-tert-butylbenzene (150ml) was added, the reaction was cooled to-20 ℃ after stirring for 20 minutes, 15mmol tert-butyllithium was added, and stirring was continued at low temperature for 30 minutes. Then gradually heating to 90 ℃ and continuously heating for 3 h. Finally, the temperature of the reaction system is reduced to-20 ℃ again, boron tribromide (5.1g, 20mmol) is added under the protection of nitrogen, and diisopropylethylamine (13g, 80mmol) is added after stirring for 30 minutes. Finally, the reaction system is heated to 110 ℃ and reacted for 12 h. After the reaction was cooled to room temperature, the organic phase was spin-dried under reduced pressure. Ethyl acetate (200ml) was extracted three times, and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 2.9g of crude product, and the crude product is recrystallized by toluene/n-hexane to obtain 1.9g of yellow solid with the purity of 99.37 percent. Mass spectrometric analysis determined molecular ion mass: 810.44 (theoretical value: 810.94).

Synthesis example 2

Synthesis of Compound M-15:

preparation of intermediate M15-1:

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

Synthesis of intermediate M15-2:

the synthesis scheme is the same as that of M5-2, namely replacing di-tert-butyl aniline with N- (2-methylphenyl) -2-methylaniline and replacing M5-1 with M15-1, and obtaining 44.7g of white solid after column chromatography.

Synthesis of compound M15:

synthesis protocol As for M5, M5-2 was replaced with M15-2(10mmol) to give 1.67g of a yellow solid of 99.41% purity. Mass spectrometric analysis determined molecular ion mass: 669.14 (theoretical value: 669.27).

Synthesis example 3

Synthesis of Compound M-35:

preparation of intermediate M35-1:

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

Stopping heating, cooling to room temperature, adding 500ml water, stirring for 10min to precipitate a large amount of white solid, filtering, and performing column chromatography to obtain 30.2g of white solid.

Synthesis of intermediate M35-2:

m35-1(43.4g, 100mmol), 3, 6-di-tert-butylaniline (45g, 160mmol), Pd was added at room temperature₂(dba)₃(1.4g, 1.5mmol), s-Phos (0.6g, 1.5mmol), sodium t-butoxide (16.8g, 175mmol), xylene (800ml) were added to a 2L single-necked flask, replaced with nitrogen three times, and heated to 130 ℃ for reaction 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 42.3g of a white solid.

Synthesis of intermediate M35-3:

m35-2(31.7g, 50mmol), 4,4' -bis (phenylisopropyl) diphenylamine (32.2g, 80mmol), Pd was added at room temperature₂(dba)₃(0.7g, 0.75mmol), s-Phos (0.3g, 0.75mmol), sodium t-butoxide (12g, 100mmol), xylene (600ml) were added to a 1L single-necked flask, replaced with nitrogen three times, and heated to 130 ℃ for reaction 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 26.2g of a white solid.

Synthesis of compound M35:

synthesis protocol As for M5, M5-2 was replaced with M35-3(10mmol) to give 1.79g of a yellow solid of 99.71% purity. Mass spectrometric analysis determined molecular ion mass: 935.14 (theoretical value: 935.07).

Synthesis example 4

Synthesis of Compound M-94

Preparation of intermediate M94-1:

alpha-phenothiazine (31.8g, 173.3mmol, 2.2eq), 1-chloro-2, 6-dibromo-4-fluorobenzene (22.4g, 78.7mmol, 1eq), cesium carbonate (118.1g, 354.1mmol, 4.5eq), N, N-dimethylformamide (600ml) were added to a 1L single-neck flask at room temperature, and reacted overnight at 120 ℃ under nitrogen.

Stopping heating, cooling to room temperature, adding 600ml water, stirring for 10min, precipitating a large amount of white solid, vacuum filtering, and performing column chromatography to obtain 26.2g of white solid.

Synthesis of intermediate M94-2:

the synthesis scheme is the same as that of M5-2, wherein M5-1 is replaced by M94-1, di-tert-butyl aniline is replaced by di-tert-butyl carbazole, and 51.2g of white solid is obtained after column chromatography.

Synthesis of compound M94:

synthesis protocol As for M5, M5-2 was replaced with M94-2(10mmol) to give 2.23g of a yellow solid of 99.47% purity. Mass spectrometric analysis determined molecular ion mass: 882.17 (theoretical value: 822.90).

The following representative specific compounds of the present invention were prepared according to the above synthetic schemes, and the mass spectrum theoretical values and the test data values of each compound are detailed in table 1 below.

Table 1:

compound numbering	Theoretical value of mass spectrum	Mass spectrometric data
			M-8	810.48	810.72
M-18	754.42	754.66
			M-25	1058.54	1058.78
M-30	934.51	934.69
			M-41	914.54	914.71
M-57	806.45	806.66
			M-65	587.22	587.36
M-68	587.22	587.29
			M-85	680.31	680.48
M-93	826.47	826.49
			M-149	698.35	698.39
M-150	698.35	698.47

Device embodiments

Detailed description of the preferred embodiments

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

In a specific embodiment, a substrate may be used under the first electrode or over the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for 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, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.

The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination 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) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may 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 is located between the HTL and the light emitting layer.

The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, 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 compounds shown below in HT-1 to HT-51; 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 a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-51 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-51 may also be used to dope one or more of the compounds HI-1-HI-3 described below.

The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.

According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.

In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, the combination of one or more of BFH-1 through BFH-17 listed below.

In one aspect of the invention, an Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but is not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described below; mixtures of one or more compounds from HT-1 to HT-51 and one or more compounds from PH-47 to PH-77 may also be used, but are not limited thereto.

The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of 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 invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-65 listed below.

In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may be, but is not limited to, one or more compounds of ET-1 to ET-65 described above, or one or more compounds of PH-1 to PH-46 described below; mixtures of one or more compounds from ET-1 to ET-65 with one or more compounds from PH-1 to PH-46 may also be used, but are not limited thereto.

An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.

LiQ,LiF,NaCl,CsF,Li₂O,Cs₂CO₃,BaO,Na,Li,Ca，Mg，Yb。

Device example 1:

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

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10^-5Pa, sequentially vacuum-thermally evaporating 10nm HT-4: HI-3(97/3, w/w) mixture as hole injection layer, 60nm compound HT-4 as hole transport layer, and 5nm compound HT-14 as hole transport layer on the anode layer filmAn electron blocking layer; a binary mixture of 20nm compounds BFH-4: M-5(100:3, w/w) is used as a light-emitting layer; 5nm of ET-23 as a hole blocking layer, 25nm of a mixture of compounds ET-61: ET-57(50/50, w/w) as an electron transport layer, 1nm of LiF as an electron injection layer, and 150nm of metallic aluminum as a cathode. The total evaporation rate of all the organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.

Device example 2 to device example 10 were fabricated in the same manner as in device example 1, except that the light-emitting dye in the light-emitting layer was replaced with the present compounds M-8, M-18, M-25, M-30, M-41, M-57, M-65, M-85, and M-137, respectively, from the present compound M-5.

Device comparative examples 1 to 3 were fabricated in the same manner as in device example 1 except that the light-emitting dye in the light-emitting layer was replaced with the compounds Ref-1, Ref-2 and Ref-3 of the prior art, respectively, by the compound M-5 of the present invention.

The testing method of the device comprises the following steps:

the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:

the driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in examples 1 to 13 and comparative examples 1 to 3 were measured at the same luminance using a digital source meter and PR 650. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m²The voltage is the driving voltage under the corresponding brightness, and the external quantum efficiency (EQE%) of the device can be directly tested on PR 650;

the life test of LT95 is as follows: using a luminance meter at 1000cd/m²The luminance drop of the organic electroluminescent device was measured to 950cd/m while maintaining a constant current at luminance²Time in hours.

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

Table 2:

as can be seen from table 2, under the condition that the material schemes and the preparation processes of other functional layers in the organic electroluminescent device structure are completely the same, the organic electroluminescent devices prepared in the device examples 1 to 13 of the present invention can effectively reduce the drop-out voltage of the device and improve the current efficiency of the device, compared with the organic electroluminescent devices prepared in the comparative examples 1 to 3. The experimental data show that the novel organic material is used as a luminescent layer material of an organic electroluminescent device, is a blue light material with good performance, and has wide application prospect.

The present invention is illustrated in detail by the examples given above, but the present invention is not limited to the details given above, which means that the present invention is not limited to the details given above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A compound of the general formula (1):

in formula (1):

ar is¹And Ar²Each independently selected from one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

Ar¹with or without rings, Ar, between adjacent rings X or Z²Form a ring or not form a ring with the adjacent ring Y or the ring Z;

and said ring X, ring Y, ring Z, Ar¹And Ar²Is substituted with a group of the structure represented by formula (G);

in the formula (G):

said X₁-X₈Each independently selected from CR¹Or N, said R¹Independently selected from one of 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is a substituent selected from the group consisting of hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1 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, and substituted or unsubstituted C3-C60 heteroaryl¹Independently linked to the linking aromatic ring to form a ring or not, and X₁-X₈Is N;

n is 0 or 1, E₁Selected from the group consisting of CR²R³、NR⁴、O、S、SiR⁵R⁶One of (1);

the R is²、R³、R⁴、R⁵And R⁶Each independently selected from hydrogen, 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 aryl, substituted or unsubstituted C,One of substituted or unsubstituted C3-C60 heteroaryl;

when the substituent exists in the groups, the substituent is selected from one or a combination of at least two of halogen, cyano, carbonyl, nitro, amino, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroaryl amino, C6-C60 monocyclic aryl or fused ring aryl, C3-C60 monocyclic heteroaryl or fused ring heteroaryl.

2. The compound of claim 1, wherein ring X, ring Y, and ring Z are each independently selected from one of a substituted or unsubstituted benzene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted carbazole ring.

3. The compound of claim 1, formula (1) wherein at least one of the ring X, ring Y is of formula (a), and/or the ring Z is of formula (b):

z is²¹～Z²³Are each independently selected from CR⁸Or N, said R⁸Independently of each otherOne 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 and substituted or unsubstituted C3-C60 heteroaryl, wherein R is selected from the group consisting of⁸Independently with the attached aromatic ring to form a ring or not; preferably the CR⁸At least one R of⁸Substituted with a group of the structure represented by formula (G).

4. The compound according to claim 3, which has a structure represented by the following formula (1-1):

ar is¹、Ar²Is the same as defined in formula (1);

5. A compound according to claim 1 or 3, formula (1), whereinAr¹And Ar²At least one of which is a structure represented by formula (c):

6. The compound of claim 5, having a structure according to formula (1-2) or formula (1-3):

ar is¹Is the same as defined in formula (1);

z is^2’～Z^4’Are each independently selected from CR¹⁰Or N, said R¹⁰Independently 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 heteroarylaminoOne of substituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, wherein R is¹⁰Independently with or without the attached aromatic ring.

7. The compound according to claim 4 or 6, wherein in the formula (1-1), formula (1-2) or formula (1-3), Z is²¹～Z²³Are each independently selected from CR⁸Or N, and wherein at least one is selected from CR⁸And wherein at least one CR is⁸R in (1)⁸A group having a structure represented by formula (G);

8. 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):

preferably, the formula (G) has a structure represented by the formula (G-1).

9. The compound according to claim 4, wherein in the formula (1-1), Z is¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

and/or, said Z^1’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

10. The compound according to claim 6, wherein in the formula (1-2), Z is¹～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷Is selected fromOne of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

still more preferably, Z is¹～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z¹～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogenOne of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^1’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen;

and/or, said Z^2’～Z^4’Are respectively and independentlySelected from the group consisting of CR¹⁰Or N, and wherein at least one is selected from CR¹⁰And wherein at least one is selected from CR¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C20 chain alkyl and substituted or unsubstituted C3-C20 cycloalkyl, and the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl;

preferably, Z is²～Z⁴Are each independently selected from CR⁷Or N, and wherein at least one is selected from CR⁷And wherein at least one is selected from CR⁷R in (1)⁷One of substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and the others are selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

still more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z²～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^2’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is³Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z²～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^3’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^2’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen;

still more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z²～Z⁴Wherein the other is selected from CR⁷R in (1)⁷One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z is^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^2’～Z^4’Wherein the others are selected from CR¹⁰R in (1)¹⁰One selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, and substituted or unsubstituted C3-C10 cycloalkyl;

more preferably, Z is²～Z⁴Are each independently selected from CR⁷And wherein Z is²Selected from the group consisting of CR⁷The CR of⁷R in (1)⁷One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z²～Z⁴Wherein the other is selected from CR⁷R in (1)⁷Selected from hydrogen;

and/or, said Z^2’～Z^4’Are each independently selected from CR¹⁰And wherein Z^2’Selected from the group consisting of CR¹⁰The CR of¹⁰R in (1)¹⁰One selected from substituted or unsubstituted C1-C10 chain alkyl and substituted or unsubstituted C3-C10 cycloalkyl, and Z^2’～Z^4’Wherein the other is selected from CR¹⁰R in (1)¹⁰Selected from hydrogen.

11. The compound according to claim 9 or 10, wherein when R is represented by formula (1-1), formula (1-2) or formula (1-3)⁷And R¹⁰When one is selected from the group consisting of substituted or unsubstituted C1-C20 chain alkyl groups and substituted or unsubstituted C3-C20 cycloalkyl groups, R⁷And R¹⁰At least one selected from the following groups:

12. the compound of claim 1, having the structure shown below:

13. use of a compound according to any one of claims 1 to 12 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;

preferably, the compound is applied to be used as a luminescent layer material in an organic electroluminescent device, particularly as a luminescent dye of a luminescent layer.

14. An organic electroluminescent 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 layers contain the compound according to any one of claims 1 to 12;

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