CN114341136B

CN114341136B - Organic compound and organic electronic device

Info

Publication number: CN114341136B
Application number: CN202080061318.4A
Authority: CN
Inventors: 张晨; 何锐锋; 萧锡辉
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2019-12-23
Filing date: 2020-12-02
Publication date: 2024-01-26
Anticipated expiration: 2040-12-02
Also published as: WO2021129337A1; CN114341136A

Abstract

The present invention relates to the field of electroluminescence, and in particular to a nitrogen-containing heterocyclic compound, an organic mixture and a composition containing the same, and application thereof in an organic electronic device. The compound can be used as a main material in electroluminescent devices, in particular OLED devices. The compound can be matched with a proper object, especially a phosphorescent object or a TADF luminophor, so that the luminous efficiency and the service life of the compound serving as an electroluminescent device can be improved, and a solution for manufacturing the luminescent device with low cost, high efficiency, long service life and low roll-off is provided.

Description

Organic compound and organic electronic device

The present application claims priority from the chinese patent office, application number 201911333160.7, entitled "an organic compound and organic electronic device," filed on date 23, 12, 2019, the entire contents of which are incorporated herein by reference.

Technical Field

The present invention relates to the field of electroluminescent materials, and in particular to a nitrogen heterocycle-based compound, organic mixtures and compositions containing the same, and the use thereof in organic electronic devices.

Background

Organic photoelectric materials have a variety of synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have advantages of wide viewing angle, fast reaction time, low operating voltage, thin panel thickness, etc. in applications of optoelectronic devices such as flat panel displays and illumination, and thus have a wide development potential.

Various luminescent material systems based on fluorescence and phosphorescence have been developed in order to improve the luminous efficiency of the organic light emitting diode, and the organic light emitting diode using the fluorescent material has a characteristic of high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric excitation because the ratio of the singlet excited state and the triplet excited state of excitons generated by current is 1:3. In contrast, organic light emitting diodes using phosphorescent materials have achieved almost 100% internal electroluminescent quantum efficiency, and thus development of phosphorescent materials has been widely studied.

The light emitting material (guest) may be used as a light emitting material together with a host material (host) to improve color purity, light emitting efficiency, and stability. The choice of host material is important because it has a great influence on the efficiency and characteristics of the electroluminescent device when a host material/guest system is used as the light-emitting layer of the light-emitting device.

Currently, 4' -dicarbazole-biphenyl (CBP) is the most widely known host material for phosphorescent substances. In recent years, a high-performance organic electroluminescent device has been developed by the japanese Pioneer company (Pioneer) and the like, which uses a compound such as BAlq (bis (2-methyl) -8-hydroxyquinolino-4-phenylphenol aluminum (III)), phenanthroline (BCP) and the like as a matrix.

In prior material designs, one has tended to use a combination of electron-transporting and hole-transporting groups to design a host for bipolar transport, which is beneficial for the balance of charge transport. The bipolar transport molecules are used as the main body, so that good device performance can be obtained. The device performance and lifetime obtained remain to be improved.

Accordingly, improvements and developments in the art, and in particular in host material solutions, are still desired.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention aims to provide N-containing condensed ring organic compounds, polymers, mixtures, compositions and applications thereof, and aims to provide a novel main material, improve the stability and service life of devices.

The technical scheme of the invention is as follows:

an organic compound represented by the general formula (1):

Wherein:

z is selected from single bond, CR ¹ R ² O, S or Ar ⁵ ；

Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ 、Ar ⁵ Each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;

R ¹ ，R ² each independently selected from H, D, a linear alkyl group having 1 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, a linear thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atomsBranched or cyclic alkoxy of 3 to 20 carbon atoms, branched or cyclic thioalkoxy group of 3 to 20 carbon atoms, silyl group of 3 to 20 carbon atoms, substituted keto group of 1 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, aryloxycarbonyl group of 7 to 20 carbon atoms, cyano group (-CN), carbamoyl group (-C (=O) NH) ₂ ) Haloformyl group, formyl group (-C (=O) -H), isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxy group, nitro group, CF ₃ A group, cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5-40 ring atoms, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

A polymer comprising at least one repeating unit comprising a structure represented by the general formula (1).

A mixture comprising at least one of the above-mentioned compounds and the above-mentioned polymers, and another organic functional material H2, wherein the another organic functional material H2 is selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting body and a host material.

A composition comprising at least one of the above-described compounds, the above-described polymers, and the above-described mixtures, and at least one organic solvent.

An organic electronic device comprising at least one of the above-described compounds, the above-described polymers, and the above-described mixtures, or prepared from the above-described compositions.

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

the organic compound can be used as a main material, and can enhance the stability of molecules and the hole transmission performance among molecules by fusing a plurality of six-membered rings or seven-membered rings at the appointed position of the nitrogen-containing five-membered ring; meanwhile, the molecules can keep proper triplet state energy level, the triplet state excitons are prevented from flowing backwards from the object to the host, the device performance is improved, and the service life of the device is prolonged. The invention provides a solution for a light emitting device with low manufacturing cost, high efficiency, long service life and low roll-off. In addition, the organic light-emitting diode is matched with a proper guest material or another host with hole transmission property or bipolar property to form a co-host, so that the electroluminescent efficiency and the service life of the device can be further improved.

Detailed Description

The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items. The invention provides an organic compound and application thereof in an organic electroluminescent device, and the invention is further described in detail below for making the purpose, technical scheme and effect of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

In the present invention, the Host material, the matrix material and the Host material have the same meaning and are interchangeable. In the embodiment of the invention, singlets have the same meaning and can be interchanged.

In the embodiments of the present invention, the triplet states have the same meaning and can be interchanged.

In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: straight chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aryl groups having 5 to 20 ring atoms, heteroaryl groups having 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, -NRR', cyano groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, nitro groups or halogen groups, and the above groups may be further substituted with art acceptable substituents selected from the group consisting of, but not limited to: a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 10 ring atoms, a heteroaryl group having 5 to 10 ring atoms, -NRR', cyano, hydroxy, trifluoromethyl, nitro or halogen; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, straight chain alkyl groups having 1-6 carbon atoms, branched or cyclic alkyl groups having 3-8 carbon atoms, heterocyclic groups having 3-8 ring atoms, aryl groups having 5-10 ring atoms, or heteroaryl groups having 5-10 ring atoms; wherein a straight chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 8 carbon atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 10 ring atoms, or a heteroaryl group having 5 to 10 ring atoms is optionally further substituted, including but not limited to the following substituents: a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 8 carbon atoms, an aryl group having 5 to 10 ring atoms (preferably phenyl or naphthyl) or a heteroaryl group having 5 to 10 ring atoms.

In the present invention, when there are a plurality of groups represented by the same symbols, the plurality of groups may be the same or different from each other, for example:several R ₁₃ May be the same or different from each other.

In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. Heteroaromatic groups refer to aromatic hydrocarbon groups containing at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. Fused ring aromatic group means that the ring of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. Fused heterocyclic aromatic groups refer to fused ring aromatic hydrocarbon groups containing at least one heteroatom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are also considered fused ring aromatic ring systems for the purposes of this invention.

Specifically, examples of condensed ring aromatic groups are: naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of fused heterocyclic aromatic groups are: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.

In the present invention, aromatic groups, aromatic ring systems have the same meaning and are interchangeable.

In the present invention, heteroaromatic groups, heteroaromatic ring systems have the same meaning and can be interchanged.

In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".

In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g R in (2) is attached to any substitutable site of the benzene ring, e.g.>Representation->Can be combined with->Optionally, a fused ring is formed at an optional position on the six-membered ring.

In the embodiment of the invention, the energy level structure of the organic material plays a key role in the triplet energy level ET1, the highest occupied orbital energy level HOMO and the lowest unoccupied orbital energy level LUMO. The determination of these energy levels is described below.

HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level ET1 of the organic material can be measured by low temperature Time resolved luminescence spectroscopy, or obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian inc.) for specific simulation methods see WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, ET ₁ Depending on the measurement method or calculation method used, even for the same method, different evaluation methods, e.g. starting points and peak points on the CV curve, may give different HOMO/LUMO values. Thus, a reasonable and meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the value of HOMO, LUMO, ET1 is based on a simulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.

The invention relates to an organic compound, which is shown in a general formula (1):

wherein:

z is selected from single bond, CR ¹ R ² O, S or Ar ⁵ ；

Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ 、Ar ⁵ Each independently selected from: a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;

R ¹ ，R ² each independently selected from: H. d, a linear alkyl radical having 1 to 20 carbon atoms, a linear alkoxy radical having 1 to 20 carbon atoms, a linear thioalkoxy radical having 1 to 20 carbon atoms, a branched or cyclic alkane having 3 to 20 carbon atomsA group, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic thioalkoxy group having 3 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted keto group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group (-CN), a carbamoyl group (-C (=o) NH) ₂ ) A haloformyl group, a formyl group (-C (=O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, and CF ₃ A group, cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5-40 ring atoms, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

In one embodiment, Z is selected from CR ¹ R ² O or S; in another embodiment, Z is selected from Ar ⁵ 。

In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ 、Ar ⁵ Each independently selected from: an aromatic group having 6 to 20 ring atoms which is substituted or unsubstituted, or a heteroaromatic group having 5 to 20 ring atoms which is substituted or unsubstituted. In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ Are each selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 6 ring atoms.

In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ At least one of them is selected from condensed ring aromatic groups or condensed ring heteroaromatic groups having 9 to 20 ring atoms. Preferably Ar ² Or Ar ³ Selected from condensed ring aromatic groups or condensed ring heteroaromatic groups with the number of ring atoms of 9-20.

In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ 、Ar ⁵ Each independently selected from any one of (A-1) to (A-8):

wherein:

x is selected from CR ³ Or N; preferably, X is selected from CR ³ The method comprises the steps of carrying out a first treatment on the surface of the When X is a connection site, X is selected from C;

Y ₁ 、Y ₂ are each independently selected from single bond, NR ³ 、CR ³ R ⁴ 、SiR ³ R ⁴ 、O、S、S(＝O) ₂ Or S (=O), Y ₁ 、Y ₂ Not simultaneously selected from single bonds;

R ³ -R ⁴ each independently selected from H, D, a linear alkyl group having 1 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, a linear thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic thioalkoxy group having 3 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted keto group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group (-CN), a carbamoyl group (-C (=O) NH ₂ ) A haloformyl group, a formyl group (-C (=O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, and CF ₃ A group, cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5-40 ring atoms, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

Further, (A-1) - (A-8) are selected from the group consisting of

Wherein: the H atom on the ring may be further replaced by R ³ And (3) substitution.

In a preferred embodiment Ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ Each independently selected from (A-1), (A-2) (A-3) or (A-4).

In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ Are all selected from (A-1); further, X is selected from CR ³ 。

In one embodiment, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ At least one of which is selected from (A-2), (A-3) or (A-4); further, ar ¹ 、Ar ² 、Ar ³ 、Ar ⁴ At least one of them is selected from (A-3)

In one embodiment, Z is selected from single bond, CR ¹ R ² O, S, (A-1) (A-2) or (A-3);

further, Z, ar ² Or Ar ³ Selected from (A-3); further, (A-3) is selected from

Further, in each embodiment, when the aromatic group and the heteroaromatic group are further substituted, the following substituents are preferably employed: straight-chain alkyl having 1 to 6 carbon atoms, branched or cyclic alkyl having 3 to 8 carbon atoms, 3 to 8 membered heterocyclyl, 5 to 10 membered aryl (preferably phenyl or naphthyl), 5 to 10 membered heteroaryl (preferably 5 to 6 membered heteroaryl), R ₀ Substituted 5-10 membered aryl, or R ₀ Substituted 5-10 membered heteroaryl; r is R ₀ Selected from: a straight chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group or a 6 membered heteroaryl group.

When the aromatic group and the heteroaromatic group are further substituted, the number of further substituted groups is not particularly limited, and each substituent may be the same or different.

In one embodiment, formula (1) is selected from any one of the structures of formulas (2-1) - (2-8):

wherein: x, Y ₁ 、Y ₂ Z has the meaning as described above. Preferably Y ₁ 、Y ₂ One of which is selected from single bonds.

In one embodiment, Z in formulas (2-1) - (2-8) is selected from single bonds; further, X is selected from CR ³ The method comprises the steps of carrying out a first treatment on the surface of the Still further, the general formulae (2-1) to (2-8) are selected from the following general formulae:

in one embodiment, formulas (2-1) - (2-8) are selected from the following formulas:

wherein Z is selected from CR ¹ R ² O or S; further, Z is selected from C (CH ₃ ) ₂ O or S.

In one embodiment, the organic compound, Z is selected from Ar ⁵ . Preferably Ar ⁵ Selected from (A-1), (A-2) or (A-3).

In one embodiment, Z is selected from:

wherein: * Represents a condensed site.

Further, Y ₁ 、Y ₂ Are each independently selected from single bond, -NPh, -C (CH) ₃ ) ₂ 、-Si(CH ₃ ) ₂ 、O、S、S(＝O) ₂ Or S (=o); y is Y ₁ 、Y ₂ Not simultaneously selected from single bonds; in one embodiment, Y ₁ O, Y of a shape of O, Y ₂ Is C (CH) ₃ ) ₂ The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, Y ₁ Is O or S, Y ₂ Is a single bond; in one embodiment, there isOrganic compound, ar ⁵ Selected from any one of the following structures:

. In one embodiment, Z is selected from (A-1); further, Z is selected from benzene and derivatives thereof.

In one embodiment, Z is selected from (A-2); further, Z is selected from naphthalene and its derivatives.

In one embodiment, Z is selected from (A-3); further, Z is selected from carbazole, dibenzothiophene, dibenzofuran, fluorene, and derivatives thereof.

Further, the general formula (1) is selected from any one of the structures of the general formulae (3-1) to (3-8):

Further, the general formulae (3-1) to (3-8) are selected from the following general formulae:

in one embodiment, the organic compound according to the present invention is selected from the following general formula:

further, Z in the general formula (4-1) or (4-2) is selected from CR ¹ R ² O or S;

further, Y in the general formula (4-3) or (4-4) ₁ Selected from O.

In one embodiment, the organic compound according to the present invention comprises at least any one of the structures (B-1) to (B-3); preferably, at leastR is R ³ Any one of the structures selected from (B-1) to (B-3):

wherein:

X ₁ selected from CR ⁵ Or N; preferably, at least one X ₁ Selected from N;

Y ₃ independently selected from NR ⁵ 、CR ⁵ R ⁶ 、SiR ⁵ R ⁶ 、O、S、S(＝O) ₂ Or S (=o);

L ₁ selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;

R ⁵ -R ⁶ each independently selected from H, D, a linear alkyl group having 1 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, a linear thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic thioalkoxy group having 3 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted keto group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group (-CN), a carbamoyl group (-C (=O) NH ₂ ) A haloformyl group, a formyl group (-C (=O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, and CF ₃ A group, cl, br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the groups R ⁵ -R ⁶ A ring which may be bonded to each other and/or to the group is a monocyclic or polycyclic aliphatic or aromatic ring; # represents the ligation site.

Advancing oneFurther, at least one R in the general formulae (2-1) to (2-8) ³ Any one of the structures selected from (B-1) to (B-3).

Further, at least one R in the general formulae (G1-1) to (G1-8) ³ Any one of the structures selected from (B-1) to (B-3).

Further, at least one R in the general formulae (G2-1) to (G2-8) ³ Any one of the structures selected from (B-1) to (B-3).

Further, at least one R in the general formulae (G3-1) to (G3-8) ³ Any one of the structures selected from (B-1) to (B-3).

Further, R in the general formulae (4-1) to (4-4) ³ Any one of the structures selected from (B-1) to (B-3).

At least one R as described in the present invention ³ R is selected from any one of structures (B-1) - (B-3) ³ From X and Y ₁ 。

In one embodiment, in the general formulae (2-2) - (2-7), (3-4) - (3-6), (3-8), (G1-4) - (G1-7), (G2-4) - (G2-7), (G3-4) - (G3-6), (G3-4), Y ₂ Selected from single bonds; more preferably, Y ₁ Selected from NR ³ The method comprises the steps of carrying out a first treatment on the surface of the Further, R ³ Any one of the structures selected from (B-1) to (B-3).

In one embodiment, (B-1) - (B-3) are selected from any of the structures (C-1) - (C-4):

in one embodiment, L in structural formulae (B-1) - (B-3) or (C-1) - (C-4) ₁ Selected from single bonds.

In one embodiment, L in structural formulae (B-1) - (B-3) or (C-1) - (C-4) ₁ Selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; more preferably L ₁ Selected from a substituted or unsubstituted aromatic group having 6 to 15 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 15 ring atoms.

In one embodiment, L ₁ Selected from the following groups:

wherein: x is X ₁ ，Y ₃ The meaning is as described above.

In one embodiment, (B-1) - (B-3) are selected from any of the following structures:

in one embodiment, R ⁵ Independently for each occurrence selected from H, a straight chain alkyl group having 1-6 carbon atoms, a branched or cyclic alkyl group having 3-8 carbon atoms, a 6-10 membered aryl group, a 6-10 membered heteroaryl group, a phenyl substituted 6-10 membered aryl group, or a phenyl substituted 6-10 membered heteroaryl group.

The organic compounds according to the present invention are listed below, but are not limited thereto:

/>

wherein: the H atom of the above structure may be further substituted.

The organic compound according to the invention can be used as a functional material in electronic devices. The organic functional materials include, but are not limited to, hole Injection Materials (HIM), hole Transport Materials (HTM), electron Transport Materials (ETM), electron Injection Materials (EIM), electron Blocking Materials (EBM), hole Blocking Materials (HBM), light emitters (Emitter), host materials (Host).

In a particularly preferred embodiment, the organic compound according to the invention is used as host material, in particular phosphorescent host material. As phosphorescent host materials, appropriate triplet energy levels, i.e.E _T1 . In certain embodiments, an N-containing compound according to the invention, E thereof _T1 Not less than 2.2eV; more preferably not less than 2.4eV, still more preferably not less than 2.6eV.

In a preferred embodiment, the organic compound according to the present invention is required to have a suitable resonance factor f (S1), which facilitates transfer of excitons from a host to a guest, and improves the light emitting efficiency of the device. Preferably, f (S1) is not less than 0.01, more preferably, f (S1) is not less than 0.05, and most preferably, f (S1) is not less than 0.08.

In another preferred embodiment, the organic compounds according to the invention are required to have a relatively suitable singlet-triplet energy level difference ΔE _ST The transfer of excitons from a host to a guest is facilitated, and the luminous efficiency of the device is improved. Preferably ΔE _ST Less than or equal to 0.9eV, more preferably delta E _ST Less than or equal to 0.6eV, preferably ΔE _ST ≤0.4eV。

When the organic compound according to the present invention is used as a host material, suitable Δhomo and Δlumo are required.

In certain preferred embodiments, the compounds ΔHOMO according to the present invention, i.e., ((HOMO- (HOMO-1)) are preferably not less than 0.1eV, more preferably not less than 0.25eV, most preferably not less than 0.40eV.

In certain preferred embodiments, the compounds ΔLUMO according to the present invention (((LUMO+1) -LUMO) are preferably not less than 0.10eV, more preferably not less than 0.20eV, most preferably not less than 0.30eV.

In certain embodiments, the organic compounds according to the invention have a luminescent function with a luminescent wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm. The term luminescence as used herein refers to photoluminescence or electroluminescence. The present invention further relates to a polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (1).

In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULMAN.

In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of not less than 100℃preferably not less than 120℃more preferably not less than 140℃more preferably not less than 160℃and most preferably not less than 180 ℃.

In a preferred embodiment, the polymers according to the invention have a molecular weight distribution (PDI) in the range from 1 to 5; more preferably 1 to 4; more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the polymers according to the invention have a weight average molecular weight (Mw) in the range from 1 to 100. Mu.m; more preferably 5 to 50 tens of thousands; more preferably 10 to 40 tens of thousands, still more preferably 15 to 30 tens of thousands, and most preferably 20 to 25 tens of thousands.

The invention also relates to a mixture comprising an organic functional material H1, H1 being selected from the group of organic compounds or polymers as described above, and at least one further organic functional material H2. The organic functional material H2 is selected from Hole Injection Materials (HIM), hole Transport Materials (HTM), electron Transport Materials (ETM), electron injection materials (ELM), electron Blocking Materials (EBM), hole Blocking Materials (HBM), luminophores (Emitter), and Host materials (Host) luminophores are selected from singlet luminophores (fluorescence luminophores), triplet luminophores (phosphorescence luminophores), especially luminescent organometallic complexes and organic thermal excitation delayed fluorescence materials (TADF materials). Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference. The organic functional material may be small molecule and high polymer materials.

In certain preferred embodiments, the organic mixture according to the invention, wherein at least one of H1 and H2 has a ΔLUMO of greater than or equal to 0.1eV, preferably greater than or equal to 0.2eV, more preferably greater than or equal to 0.2eV.

In a preferred embodiment, the organic mixture according to the invention, wherein ΔLUMO of H1 is not less than 0.1eV, preferably not less than 0.2eV, more preferably not less than 0.3eV.

In certain preferred embodiments, the organic mixture according to the invention, wherein at least one of H1 and H2 has a ΔHOMO of 0.1eV or more, preferably 0.25eV or more, more preferably 0.4eV or more.

In a preferred embodiment, the organic mixture according to the invention has a ΔHOMO of H2 of 0.1eV or more, preferably 0.25eV or more, more preferably 0.4eV or more.

In certain preferred embodiments, the organic mixture wherein min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)). Ltoreq.min (ET (H1), ET (H2)) +0.1eV, wherein LUMO (H1), HOMO (H1) and ET (H1) are each the lowest unoccupied orbital of H1, the highest occupied orbital, the energy level of the triplet state, LUMO (H2), HOMO (H2) and ET (H2) are each the lowest unoccupied orbital of H2, the highest occupied orbital, the energy level of the triplet state, preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)). Ltoreq.min (ET (H1), more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)). Ltoreq.min (E) _T (H1)，E _T (H2))-0.1eV；

In certain preferred embodiments, the organic mixture wherein 1) ΔE (S1-T1) of H1 is less than or equal to 0.60eV, preferably less than or equal to 0.44eV, more preferably less than or equal to 0.37eV, and most preferably less than or equal to 0.10eV, and/or 2) the LUMO of H2 is higher than the LUMO of H1 and the HOMO of H2 is lower than the HOMO of H1.

In a preferred embodiment, the organic mixture, wherein the molar ratio of H1 to H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; more preferably in a molar ratio of 4:6 to 6:4; the most preferred molar ratio is 5:5.

In a preferred embodiment, the organic mixture wherein the difference in molecular weight between H1 and H2 is not more than 100Dalton, preferably not more than 80Dalton, more preferably not more than 60Dalton, very preferably not more than 40Dalton, most preferably not more than 30Dalton.

In another preferred embodiment, the organic mixture, wherein the difference in sublimation temperatures of H1 and H2 is no more than 50K; more preferably, the difference in sublimation temperature does not exceed 30K; more preferably, the difference in sublimation temperature does not exceed 20K; most preferably the difference in sublimation temperature does not exceed 10K. In a preferred embodiment, at least one of H1 and H2 in the organic mixture according to the invention has a glass transition temperature Tg of greater than or equal to 100deg.C, in a preferred embodiment at least one has a Tg of greater than or equal to 120deg.C, in a more preferred embodiment at least one has a Tg of greater than or equal to 140deg.C, in a more preferred embodiment at least one has a Tg of greater than or equal to 160deg.C, and in a most preferred embodiment at least one has a Tg of greater than or equal to 180deg.C.

In a preferred embodiment, the mixture comprises at least one N-containing organic compound or polymer according to the invention and a luminescent material selected from the group consisting of singlet emitters, triplet emitters and TADF emitters.

In certain embodiments, the mixture comprises at least one organic compound or polymer according to the invention and a singlet emitter, wherein the singlet emitter comprises 10 wt.% or less, preferably 9 wt.% or less, more preferably 8 wt.% or less, particularly preferably 7 wt.% or less, and most preferably 5 wt.% or less.

In a particularly preferred embodiment, the mixture comprises at least one organic compound or polymer according to the invention and a triplet emitter, wherein the triplet emitter weight percent is 25 wt.% or less, preferably 20 wt.% or less, more preferably 15 wt.% or less. In a further preferred embodiment, the mixture comprises at least one N-containing organic compound or polymer according to the invention, a triplet emitter and a host material. In such an embodiment, the N-containing organic compounds according to the invention can be used as auxiliary light-emitting materials in a weight ratio to triplet emitters of from 1:2 to 2:1. In a further preferred embodiment, the exciplex of the mixture according to the invention has an energy level which is higher than that of the phosphorescent emitter.

In another more preferred embodiment, the mixture comprises at least one N-containing organic compound or polymer according to the invention, and a TADF material, wherein the weight percent of the TADF host material is less than or equal to 15 wt.%, preferably less than or equal to 10 wt.%, more preferably less than or equal to 5 wt.%.

In a very preferred embodiment, the mixture comprises an N-containing organic compound according to the invention, and a further host material. The organic compound according to the invention may be used as the second body in an amount of 30 to 70% by weight.

In the present invention, the details of the singlet state light emitter, the triplet state light emitter, the TADF material and the host material are described in patent WO2018095390A1.

In certain preferred embodiments, the mixture further organic functional material H2 comprises a structural formula as shown in structural formula (7) or (8):

wherein:

R ₁₃ selected from H, D, straight-chain alkyl having 1 to 20 carbon atoms, straight-chain alkoxy having 1 to 20 carbon atoms, straight-chain thioalkoxy having 1 to 20 carbon atoms, branched or cyclic alkyl having 3 to 20 carbon atoms, branched or cyclic alkoxy having 3 to 20 carbon atoms, branched or cyclic thioalkoxy having 3 to 20 carbon atoms, silyl having 3 to 20 carbon atoms, substituted keto having 1 to 20 carbon atoms, alkoxycarbonyl having 2 to 20 carbon atoms, aryloxycarbonyl having 7 to 20 carbon atoms, cyano (-CN), carbamoyl, haloformyl, formyl, isocyanato, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, cl, br, F, crosslinkable groups, substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, aromatic groups having 5 to 40 ring atoms An oxy or heteroaryloxy group or a combination of these systems or formula (8); and at least one R ₁₃ Has a structure shown in a structural formula (8);

Ar ⁶ ，Ar ⁷ each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring group having 5 to 30 ring atoms;

L ₂ selected from a single bond, a substituted or unsubstituted aryl group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic cyclic group having 5 to 30 ring atoms;

Ar ⁶ ，Ar ⁷ ，L ₂ any two adjacent groups of (a) may be linked to each other to form a ring.

Further, H2 is selected from the following formulae:

in one embodiment, formula (8) may be selected from the structures shown in formula (9):

wherein: # represents the ligation site.

In certain preferred embodiments, H2 is selected from the following formulas:

in certain preferred embodiments, L ₂ Is thatm is 1, 2, 3, 4 or 5; further, m is 2;

in certain preferred embodiments, R ₁₃ Selected from H,R ₁₄ Is H, 5-10 membered aryl or 5-10 membered heteroaryl. Further, R ₁₄ Is H, phenyl or naphthyl, further R ₁₃ Selected from H, & lt>

Preferably, the organic functional material H2 is selected from the following structures, but is not limited thereto, wherein H in the structures may be further optionally substituted.

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It is an object of the present invention to provide a material solution for an evaporated OLED.

In certain embodiments, the organic compounds according to the present invention have a molecular weight of 1200g/mol or less, preferably 1100g/mol or less, more preferably 1000g/mol or less, more preferably 950g/mol or less, and most preferably 900g/mol or less.

It is another object of the invention to provide a material solution for printed OLEDs.

In certain embodiments, the organic compounds according to the present invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, more preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.

In other embodiments, the organic compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.

The invention also relates to a composition comprising at least one organic compound or polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, borate or phosphate compound, or mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that the at least one organic solvent is chosen from aromatic or heteroaromatic based solvents.

Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;

Examples of aromatic ketone-based solvents suitable for the present invention are, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-thiopyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the composition according to the invention, said at least one solvent may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred embodiments, the at least one solvent according to the compositions of the present invention may be chosen from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate.

The solvent may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are solvents having Hansen (Hansen) solubility parameters within the following ranges:

δ _d (dispersion force) of 17.0-23.2 MPa ^1/2 In particular in the range from 18.5 to 21.0MPa ^1/2 Is defined by the range of (2);

δ _p (polar force) is 0.2-12.5 MPa ^1/2 In particular in the range of 2.0 to 6.0MPa ^1/2 Is defined by the range of (2);

δ _h the (hydrogen bond force) is between 0.9 and 14.2MPa ^1/2 In particular in the range of 2.0 to 6.0MPa ^1/2 Is not limited in terms of the range of (a).

The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; and most preferably at a temperature of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions according to embodiments of the invention may comprise from 0.01 to 10% by weight of the organic compound or polymer or mixture according to the invention, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 5% by weight, most preferably from 0.25 to 3% by weight.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by printing or coating.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. For details on printing techniques and their related requirements for solutions, such as solvents and concentrations, viscosities, etc., see the handbook of printing media, by Helmut Kipphan: techniques and methods of production (Handbook of Print Media: technologies and Production Methods), ISBN 3-540-67326-1.

The invention also provides the use of an organic compound, polymer, mixture or composition as described above in an organic electronic device selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), and the like, particularly preferably OLEDs. In the embodiment of the invention, the N-containing organic compound or the high polymer is preferably used for a light-emitting layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one organic compound, polymer or mixture as described above. Generally, such an organic electronic device comprises at least one cathode, one anode and one functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above. The organic electronic device may be selected from, but not limited to, organic Light Emitting Diode (OLED), organic photovoltaic cell (OPV), organic light emitting cell (OLEEC), organic Field Effect Transistor (OFET), organic light emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and particularly preferably organic electroluminescent devices such as OLED, OLEEC, organic light emitting field effect transistor.

In certain preferred embodiments, the light-emitting layer of the electroluminescent device comprises an organic compound or mixture or polymer as described above.

In certain preferred embodiments, the light-emitting layer of the electroluminescent device comprises an organic compound as described above, or comprises an organic compound as described above and a phosphorescent light-emitting material, or comprises an organic compound as described above and a host material, or comprises an organic compound as described above and a TADF material.

In the light emitting device, especially the OLED, the light emitting device comprises a substrate, an anode, at least one light emitting layer and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996, 380, p29, and Gu et al, appl. Phys. Lett.1996, 68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF ₂ /Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.

The light emitting device according to the present invention has a light emitting wavelength of 300 to 1200nm, preferably 350 to 1000nm, more preferably 400 to 900 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The invention will be described in connection with the preferred embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims summarize the scope of the invention and those skilled in the art who have the benefit of this disclosure will recognize certain changes that may be made to the embodiments of the invention and that are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The synthetic methods of the compounds according to the present invention are exemplified, but the present invention is not limited to the following examples.

Example 1

1-3: 1-1 (15.0 g), 1-2 (13.5 g), pd (PPh) ₃ ) ₄ (0.5 g) and potassium carbonate (12.9 g) were added to 200ml of a 1, 4-dioxane/water (volume ratio: 8:1) mixed solvent, and refluxed under a nitrogen atmosphere for 12 hours. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining material was extracted with dichloromethane and washed three times with water. The organic phase was collected, the solvent was removed by rotary evaporation, and the crude product obtained was subjected to column chromatography to give 1-3.MS (ASAP): 482.40.

1-4: 1-3 (15.0 g), pinacol diboronate (7.9 g), pd (dppf) Cl ₂ (0.5 g), potassium acetate (6.1 g) was added to 1, 4-dioxane (120 m 1). Reflux for 8h under nitrogen atmosphere. After cooling, the reaction solution was concentrated by distillation under reduced pressure, followed by recrystallization to give intermediates 1 to 4.MS (ASAP): 447.32.

synthesis of 1-6 1-4 (10.0 g), 1-5 (5.4 g), pd (PPh) ₃ ) ₄ (0.2 g) and potassium carbonate (5.5 g) were added to 150ml of a 1, 4-dioxane/water (volume ratio: 8:1) mixed solvent, and refluxed under a nitrogen atmosphere for 12 hours. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining material was extracted with dichloromethane and washed three times with water. The organic phase was collected, the solvent was removed by rotary evaporation, and the crude product obtained was purified by column chromatography to give 1-6.MS (ASAP): 608.13.

1-7: 1-6 (8.0 g) and cesium carbonate (8.6 g) were dissolved in 150ml DMF and stirred at 140℃for 6h. After cooling, the reaction solution was concentrated by distillation under reduced pressure, and the residue was extracted with dichloromethane and washed three times with water, and the organic phase was collected. The organic phase is distilled off by spin to remove the solvent and recrystallized to obtain 1-7.MS (ASAP): 588.13.

synthesis of material 1: 1-7 (5.0 g) was dissolved in 120ml DMAC and Pd (OAc) was added ₂ (0.1g)、P(Cy ₃ )·HBF ₄ (0.44 g) and cesium carbonate (5.5 g). The reaction was carried out at 145℃for 12h under nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure. Pouring the residual reaction liquid into a large amount of water, and filtering to obtain a filter cake. Recrystallizing the filter cake to obtain a material 1.MS (ASAP): 588.13.

Example 2

2-3: 2-1 (8.0 g), 2-2 (10.2) and cesium carbonate (31.5 g) were dissolved in 100ml of DMF and stirred at 120℃for 12h. After cooling, the reaction mixture was concentrated by distillation under reduced pressure, washed with water, and extracted with dichloromethane. The organic phase is distilled off by rotating to remove the solvent and then recrystallized to obtain 2-3.MS (ASAP): 356.65.

2-5 synthesis referring to synthesis of 1-6, except that 1-4 is replaced with 2-4 and 1-5 is replaced with 2-3.MS (ASAP): 388.29. 2-6: 2-5 (10.0 g) was dissolved in 120ml DMAC and Pd (OAc) was added ₂ (0.5 g), tricyclohexylphosphine tetrafluoroborate (1.9 g), and cesium carbonate (25.2 g). The reaction was carried out for 20h at 145℃under nitrogen. After cooling, most of the solvent was distilled off under reduced pressure. The remaining reaction solution was extracted with dichloromethane and washed three times with water. The organic phase is collected and subjected to column chromatography to obtain 2-6.MS (ASAP): 315.38.

2-7: 2-6 (7.0 g) was dissolved in dichloromethane and NBS (1.2 g) was slowly added dropwise while stirring at room temperature in the absence of light. Then stirred at room temperature for 2h. After the reaction is finished, separating the reaction liquid by water, removing the solvent by rotary evaporation of an organic phase, and obtaining 2-7 after column chromatography. MS (ASAP): 394.27.

2-8 with reference to the synthesis of 1-4, except that 1-3 is replaced with 2-7.MS (ASAP): 441.34.

Synthesis of material 2 refers to synthesis of 1-3, except that 1-1 is replaced with 2-8 and 1-2 is replaced with 2-9.MS (ASAP): 575.69.

example 3

3-2 synthesis referring to the synthesis of 2-3, except that 2-2 was replaced with 3-1.MS (ASAP): 401.10.

synthesis of 3-3A mixture of 3-2 (15.0 g), 2-4 (11.7 g), pd (PPh) ₃ ) ₄ (0.3 g) and potassium carbonate (15.5 g) were added to 200ml of a 1, 4-dioxane/water (volume ratio: 8:1) mixed solvent, and refluxed under a nitrogen atmosphere for 12 hours. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining material was extracted with dichloromethane and washed three times with water. The organic phase is collected, the solvent is removed by rotary evaporation, and the obtained crude product is purified by column chromatography to obtain 3-3.MS (ASAP): 464.39.

3-4 with reference to the synthesis of 2-6, except that 2-5 is replaced with 3-3.MS (ASAP): 391.47.

3-5 with reference to the synthesis of 2-7, except that 2-6 was replaced with 3-4.MS (ASAP): 470.37.

3-6 with reference to the synthesis of 1-4, except that 1-3 is replaced with 3-5.MS (ASAP): 517.44.

synthesis of material 3 refers to synthesis of 1-3, except 1-1 is replaced with 3-6 and 1-2 is replaced with 3-7.MS (ASAP): 622.73.

example 4

4-3 synthesis referring to the synthesis of 1-3, except that 1-1 was replaced with 4-1 and 1-2 was replaced with 4-2.MS (ASAP): 466.34.

4-4 synthesis referring to the synthesis of 1-4, except that 1-3 is replaced with 4-3.MS (ASAP): 513.40.

4-6 synthesis referring to the synthesis of 1-6, except that 1-4 is replaced with 4-4 and 1-5 is replaced with 4-5.MS (ASAP): 642.13.

4-7 synthesis referring to the synthesis of 1-7, except that 1-6 was replaced with 4-6.MS (ASAP): 622.12.

synthesis of Material 4 reference was made to the synthesis of Material 1, except that 1-7 was replaced with 4-7.MS (ASAP): 585.67.

example 5

5-2 synthesis referring to the synthesis of 1-3, except that 1-1 was replaced with 5-1 and 1-2 was replaced with 3-7.MS (ASAP): 398.47.

5-3 with reference to the synthesis of 2-3, except that 2-1 was replaced with 5-2 and 2-2 was replaced with 3-1.MS (ASAP): 632.06.

5-4 synthesis: 5-3 (14.0 g), pinacol diboronate (11.3 g), pd (dppf) Cl ₂ (0.5 g), potassium acetate (6.6 g) was added to 1, 4-dioxane (180 ml). Reflux under nitrogen for 8h. After cooling, most of the solvent was removed by rotary evaporation, and the crude product obtained was recrystallized to give intermediate 5-4.MS (ASAP): 726.49.

5-6: 5-4 (10.0 g), 5-5 (6.1 g), pd (PPh) ₃ ) ₄ (0.5 g) and potassium carbonate (5.7 g) were added to 200ml of a 1, 4-dioxane/water (volume ratio: 8:1) mixed solvent, and refluxed under a nitrogen atmosphere for 6 hours. After cooling, most of the solvent was distilled off under reduced pressure, the remaining material was extracted with dichloromethane and washed three times with water, the organic phase was collected, the solvent was removed by rotary evaporation, and recrystallization was performed to obtain 5-6.MS (ASAP): 799.72. synthesis of material 5 refers to synthesis of 2-6, except that 2-5 is replaced with 5-6.MS (ASAP): 726.80.

Example 6

6-2 synthesis: 6-1 (15.0 g), 3-7 (10.9 g) were dissolved in 140ml of dry DMSO, DMAP (1.6 g), cesium carbonate (26.7 g) were added, and the mixture was refluxed at 140℃for 6 hours. After cooling, most of the solvent was distilled off under reduced pressure, and the concentrated reaction solution was poured into a large amount of water and stirred for 30min. Suction filtration is carried out, and the filter cake is recrystallized and purified to obtain 6-2.MS (ASAP): 598.52.

6-4 synthesis refers to synthesis of 1-3, except that 1-1 is replaced with 6-3 and 1-2 is replaced with 6-2.MS (ASAP): 724.25.

6-5 synthesis referring to the synthesis of 1-7, except that 1-6 was replaced with 6-4.MS (ASAP): 704.25.

synthesis of material 6 reference is made to the synthesis of material 1, except that 1-7 is replaced with 6-5.MS (ASAP): 667.79.

example 7

7-3 synthesis: 7-1 (15.0 g), 7-2 (6.0 g) were dissolved in 120ml of o-xylene, and copper powder (120 mg), cuCl (180 mg), 1, 10-phenanthroline (330 mg) and cesium carbonate (3.5 g) were added. Stirring is carried out for 24h at 150℃under nitrogen. Cooling, filtering, distilling under reduced pressure to remove most of solvent, and purifying concentrated reaction liquid by column chromatography to obtain 7-3.MS (ASAP): 729.65.

7-4 synthesis refers to the synthesis of 1-6, except that 1-4 is replaced with 2-3 and 1-5 is replaced with 7-3.MS (ASAP): 716.30

7-5 synthesis reference material 1 was synthesized except that 1-7 was replaced with 7-4.MS (ASAP): 724.84.

synthesis of material 7: 7-5 (10.0 g) was dissolved in dry THF (100 ml), and methyl magnesium bromide (1M, 28 ml) was slowly added dropwise at 0℃under nitrogen. After the completion of the dropwise addition, stirring was continued and gradually returned to room temperature, and stirring was continued for 3 hours. After the reaction, water is added to quench the reaction, and the mixture is extracted and separated by water washing. The organic phase was collected, the solvent was removed by rotary evaporation, and the resulting crude product was poured into 100ml of acetic acid and stirred at 80℃for 6 hours. After cooling, the solvent is distilled off under reduced pressure to remove most of the solvent, the concentrated reaction solution is poured into water, the pH is adjusted to be neutral by adding alkaline solution, and the reaction solution is extracted by dichloromethane and washed with water for a plurality of times. The organic phase was collected, and the solvent was removed by rotary evaporation and recrystallized to give material 7.MS (ASAP): 706.87.

example 8

8-1 synthesis refers to the synthesis of 1-6, except that 1-4 is replaced with 8-1 and 1-5 is replaced with 8-2.MS (ASAP): 665.17.

8-4 with reference to the synthesis of 1-7, except that 1-6 was replaced with 8-3.MS (ASAP): 646.15.

synthesis of Material 8 reference the synthesis of Material 1 except that 1-7 was replaced with 8-4.MS (ASAP): 609.69.

Example 9

9-3 synthesis referring to the synthesis of 1-6, except that 1-4 was replaced with 9-1 and 1-5 was replaced with 9-2.MS (ASAP): 504.02.

9-4 synthesis referring to the synthesis of 1-7, except that 1-6 was replaced with 9-3.MS (ASAP): 484.01.

9-5, except that 1-7 is replaced with 9-4.MS (ASAP): 447.56.

9-6 synthesis referring to the synthesis of 2-7, except that 2-6 was replaced with 9-5.MS (ASAP): 526.45.

9-7 synthesis referring to the synthesis of 1-4, except that 1-3 was replaced with 9-7.MS (ASAP): 573.52.

synthesis of material 9 refers to synthesis of 1-3, except 1-1 is replaced with 9-7 and 1-2 is replaced with 9-8.MS (ASAP): 691.81.

example 10

10-1 with reference to the synthesis of 1-6, except that 1-4 was replaced with 2-4 and 1-5 was replaced with 3-2.MS (ASAP): 419.73.

10-3 with reference to the synthesis of 1-6, except that 1-4 was replaced with 10-2 and 1-5 was replaced with 10-1.MS (ASAP): 596.55.

synthesis of material 10 refers to the synthesis of 2-6, except that 2-5 is replaced with 10-3.MS (ASAP): 523.64.

example 11

11-3 with reference to the synthesis of 1-6, except that 1-4 is replaced with 11-2 and 1-5 is replaced with 11-1.MS (ASAP): 769.28.

11-4 with reference to the synthesis of 1-7, except that 1-6 was replaced with 11-3.MS (ASAP): 749.27.

synthesis of Material 11 reference the synthesis of Material 1 except that 1-7 was replaced with 11-4.MS (ASAP): 712.81.

example 12

12-3 with reference to the synthesis of 1-6, except that 1-4 was replaced with 12-2 and 1-5 was replaced with 12-1.MS (ASAP): 884.46.

12-4 with reference to the synthesis of 1-7, except that 1-6 was replaced with 12-3.MS (ASAP): 864.45.

synthesis of Material 12 reference the synthesis of Material 1 except that 1-7 was replaced with 12-4.MS (ASAP): 827.99.

example 13

13-2 with reference to the synthesis of 1-6, except that 1-4 was replaced with 13-1 and 1-5 was replaced with 11-1.MS (ASAP): 819.34.

13-3 with reference to the synthesis of 1-7, except that 1-6 was replaced with 13-2.MS (ASAP): 799.33.

synthesis of Material 13 reference the synthesis of Material 1 except that 1-7 was replaced with 13-3.MS (ASAP): 762.87.

2. organic compound energy level calculation

The energy level of the organic compound material can be obtained by quantum computation, for example by means of a Gaussian09W (Gaussian inc.) using TD-DFT (time-dependent density functional theory), and specific simulation methods can be seen in WO2011141110. The molecular geometry is first optimized by the Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin single), and then the energy structure of the organic molecule is calculated by the TD-DFT (time-Density functional theory) method as "TD-SCF/DFT/Default Spin/B3PW91" and the basis set "6-31G (d)" (Charge 0/Spin single). The HOMO and LUMO energy levels were calculated according to the following calibration formula, S ₁ ，T ₁ And a resonance factor f (S ₁ ) Is directly used.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Wherein HOMO (G) and LUMO (G) are direct calculations of Gaussian 09W in Hartree. The results are shown in Table one:

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as shown in table 1, LUMO energy levels of materials 1 to 9 and 11 to 13 are all in the range of-2.78 to-2.98 eV, and the materials can be used for an electron-type host material; the HOMO energy levels of the materials 1, 3, 4, 6, 7, 9 and 13 are in the range of-5.31 to-5.66 eV, and the material can be used as a cavity type host material; the triplet energy levels of materials 1 through 13 are all higher than 2.20eV, indicating that these materials can all be used as red host materials. H2-1 and H2-2 are two materials meeting the general formula of H2 in the invention.

Material 2, material 3, material 5, material 6, material 8, material 11 through material 13 are blended with H2-1, respectively, or material 2, material 3, material 11 are blended with H2-2, respectively, all satisfying the condition that min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)). Ltoreq.min (ET (H1), ET (H2)) +0.1eV, indicating that mixtures of these materials with H2-1 or H2-2 can form an exciplex as a co-host material.

3. Device fabrication and inspection

Device example 1

The device structure is ITO/HATCN/HTM/host material (material 1): RD/ETM: liq/Liq/Al. Wherein the mass ratio of the host material to RD is 95:5. The preparation process is as follows:

a. Cleaning the conductive glass substrate: when the cleaning agent is used for the first time, various solvents such as chloroform, ketone and isopropanol can be used for cleaning, and then ultraviolet ozone plasma treatment is carried out;

b. HATCN (30 nm), HTM (50 nm), host material: RD (40 nm), ETM: liq (30 nm), liq (1 nm), al (100 nm) under high vacuum (1×10) ^-6 Millibar) by thermal evaporation;

c. and (3) packaging: the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.

Preparation of OLED devices referring to device example 1, the host materials were replaced by the compounds shown in Table 2 or by a 1:1 blend mixture.

Table 2: comparison of OLED device Performance

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The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 2 shows the lifetime and external quantum efficiency comparisons of OLED devices, where lifetime LT95 is the time at which luminance drops to 95% of the initial luminance @1000nits at constant current. Here, LT95, external quantum efficiency was calculated relative to device example 14 (corresponding to comparative example 1), i.e., with the lifetime of device example 14 being 1, external quantum efficiency being 100.

As can be seen from table 2, the external quantum efficiency and lifetime of devices of device examples 1 to 13 were significantly higher than those of device example 14 (the host material is comparative example 1). The material disclosed by the invention has a seven-membered ring conjugated system with electron donating property and electron withdrawing substituent, so that the material has balanced hole and electron transporting capacity, and the material of the comparative example lacks electron withdrawing substituent to cause unbalanced hole and electron transporting; meanwhile, the HOMO levels of materials 1 to 13 were lower than those of comparative example 1 (-5.14 eV), which is another reason why the device efficiency and lifetime of device examples 1 to 13 were higher than those of comparative examples. Among them, the device lifetime of device examples 3 to 13 was significantly higher than that of the other single host examples (corresponding to device examples 1 and 2), because the compounds used in these examples had a larger condensed ring system and better stability, and the carrier transport ability between molecules was better.

Device example 17 (corresponding to a mixture of materials 6: H2-1 in a mass ratio of 1: 1) and device example 18 (corresponding to a mixture of materials 11: H2-2 in a mass ratio of 1: 1) which employed the mixture of the present invention as a co-host had relatively higher device lifetime and external quantum efficiency (both exceeding 25%) because the co-host had relatively more balanced hole/electron transport properties and an exciplex with TADF effect was formed in the energized state, increasing exciton utilization efficiency. Therefore, the luminous efficiency and the service life of the OLED device prepared by the organic mixture are obviously improved.

Claims

1. An organic compound characterized by being represented by any one of the following general formulas:

wherein:

z is selected from C (CH) ₃ ) ₂ O or S;

wherein R is ³ Is H;

Y ₁ independently selected from: c (CH) ₃ ) ₂ O or S.

2. An organic compound, characterized in that the organic compound is selected from any one of the following structures:

3. a polymer characterized in that: comprising at least one repeating unit comprising the organic compound of any one of claims 1-2.

4. A mixture characterized by: comprising an organic functional material H1, the H1 being selected from at least one of the organic compound according to any one of claims 1 to 2 and the polymer according to claim 3, and another organic functional material H2, the other organic functional material H2 being selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting body, and a host material.

5. The mixture according to claim 4, wherein: min ((LUMO (H1) -HOMO (H2)), LUMO (H2) -HOMO (H1)). Ltoreq.min (ET (H1), ET (H2)) +0.1eV, wherein LUMO (H1) refers to the lowest unoccupied orbital of H1, HOMO (H1) refers to the highest occupied orbital of H1, ET (H1) refers to the energy level of the triplet state of H1, LUMO (H2) refers to the lowest unoccupied orbital of H2, HOMO (H2) refers to the highest occupied orbital of H2, ET (H2) refers to the energy level of the triplet state of H2.

6. A composition characterized by: comprising at least one of the organic compounds according to any of claims 1 to 2, the polymers according to claim 3, and the mixtures according to any of claims 4 to 5, and at least one organic solvent.

7. An organic electronic device, characterized in that: comprising the organic compound according to any one of claims 1 to 2, the polymer according to claim 3, at least one of the mixtures according to any one of claims 4 to 5, or prepared from the composition according to claim 6.