CN112794856B

CN112794856B - Organic compounds, mixtures, compositions and uses thereof

Info

Publication number: CN112794856B
Application number: CN202011139370.5A
Authority: CN
Inventors: 黄宏
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2019-11-14
Filing date: 2020-10-22
Publication date: 2022-10-04
Anticipated expiration: 2040-10-22
Also published as: CN112794856A

Abstract

The invention relates to an organic compound, a mixture, a composition and application thereof, wherein the organic compound is selected from a structure shown as a general formula (1), according to the organic compound, an aromatic ring and two seven-membered rings on carbazole are fixed in the same molecular plane, so that the rigidity of material molecules is improved, the stability of the material is improved, and when a luminescent device is prepared by using the organic compound, the service life of the device can be prolonged. The organic compound can be used as red and green light phosphorescence host materials, can improve the luminous efficiency and the service life of an electroluminescent device by matching with proper guest materials, and provides a technical scheme for preparing the luminous device with low cost, high efficiency, long service life and low roll-off.

Description

Organic compounds, mixtures, compositions and uses thereof

The present application claims priority from the chinese patent application having the title "an organic compound containing a seven-membered ring and its use" filed by the chinese patent office on 14/11/2019 under application No. 201911111644.7, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to an organic compound, a polymer, a mixture, a composition and application thereof, especially application in an organic electroluminescent device.

Background

Organic light emitting materials have a variety of synthetic, relatively low manufacturing costs and excellent optical and electrical properties, and Organic Light Emitting Diodes (OLEDs) made from organic light emitting materials have great potential for applications in optoelectronic devices such as flat panel displays and lighting.

To date, a luminescent material system based on fluorescence and phosphorescence has been developed, and an organic light emitting diode using a fluorescent material has a high reliability, but its internal electroluminescence quantum efficiency under electrical excitation is limited to 25% because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency. However, the stability of phosphorescent OLEDs is still to be improved. The stability of OLEDs, in addition to the emitter itself, is critical for the host material.

For red and green phosphorescent light-emitting devices, the performance of a host material determines the efficiency and the service life of the red and green phosphorescent light-emitting devices, and currently, the commonly used host material is an organic compound containing a carbazole group, but the charge transport of the material is unbalanced and the stability is limited, so that the service life of the device is not high. Researchers have been working on developing organic light emitting materials with good stability, but the stability of the organic light emitting materials developed at present is still insufficient.

Therefore, the design and synthesis of the organic luminescent material with good stability are of great significance.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide an organic compound, a polymer, a mixture, a composition, an organic electronic device and an application thereof, which aim to solve the problems of insufficient stability and rigidity of the existing host luminescent material.

The technical scheme of the invention is as follows:

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

wherein:

Ar ¹ -Ar ⁴ each independently selected from a substituted or unsubstituted aromatic group containing 6 to 60C atoms or a substituted or unsubstituted heteroaromatic group containing 5 to 60 ring atoms or a substituted or unsubstituted non-aromatic ring system containing 3 to 30 ring atoms;

X ₁ ～X ₃ at each occurrence, is independently selected from none, or CR ₁ R ₂ ，SiR ₁ R ₂ ，NR ₁ ，C(＝O)，S，S(＝O) ₂ And O; wherein X ₁ ～X ₃ At most one of which is selected from none;

R ₁ -R ₂ independently at each occurrence, is selected from H, D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms or a linear thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, CF, a formyl group, an isocyanato group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ Cl, br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or from 5 toAn aryloxy or heteroaryloxy group of 60 ring atoms, or a combination of these systems.

The invention further relates to a mixture comprising an organic compound as described above, and at least one organic functional material, which may be selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, or a host material.

The invention also relates to a composition comprising an organic compound or mixture as described above, and at least one organic solvent.

The invention further relates to an organic electronic device comprising at least one organic compound or mixture or composition as described above.

Has the advantages that:

according to the organic compound, the aromatic ring and the two seven-membered rings on the carbazole are fixed in the same molecular plane, so that the rigidity of the molecule is improved, the stability of the material is improved, and the service life of the device can be prolonged when the organic compound is used for preparing a light-emitting device. The organic compound can be used as a red light phosphorescence host material, can improve the luminous efficiency and the service life of an electroluminescent device by matching with a proper guest material, and provides a technical scheme for preparing the luminescent device with low cost, high efficiency, long service life and low roll-off.

Detailed Description

The invention provides an organic compound, a polymer, a mixture, a composition and application thereof. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, "substituted" means that a hydrogen atom in a substituent 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 thatOptionally substituted with art-acceptable groups including, but not limited to: c _1-30 An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted by a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C _1-6 An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is _1-6 Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c _1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a fused ring compound, a crosslinked compound, a carbocyclic compound, and 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 "number of ring atoms" described below is the same 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. A heteroaromatic group refers to an aromatic hydrocarbon group that contains 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. By fused ring aromatic group is meant that the rings 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. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems.

Thus, for example, 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 systems of aromatic or heteroaromatic groups, 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-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

In a certain preferred embodiment, the aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primadines, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.

In the present invention, "+" attached to a single bond represents a connection site or a fusion site.

In the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site.

In the present invention, when the condensed site is not specified in the group, it means that an optionally condensable site in the group is a condensed site, and preferably two or more sites at the ortho position in the group are condensed sites.

In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example

Wherein R is attached to any substitutable site of the phenyl ring.

In the embodiment of the invention, the energy level structure of the organic material, the triplet state energy level E _T HOMO and LUMO play key roles. The energy levels are described below.

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

Triplet energy level E of organic material _T1 Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E _T1 The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably 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, HOMO, LUMO, E _T1 Is based on a simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO + 1) is defined as the second lowest unoccupied orbital level, (LUMO + 2) is the third lowest occupied orbital level, and so on.

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

wherein:

Ar ¹ -Ar ⁴ each independently selected from substituted or unsubstituted aromatic groups containing 6 to 60C atoms or heteroaromatic groups containing 5 to 60 ring atoms or non-aromatic ring systems containing 3 to 30 ring atoms;

R ₁ -R ₂ each occurrence is independently selected from H, D, or a linear alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms or a thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, CF ₃ A Cl, br, F, I crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

In a certain preferred embodiment, ar ¹ -Ar ⁴ Independently selected from substituted or unsubstituted aromatic groups containing 6 to 30C atoms or heteroaromatic groups containing 5 to 30 ring atoms.

In a certain preferred embodiment of the present invention,Ar ¹ -Ar ⁴ at least one of them is selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 60C atoms or fused ring heteroaromatic groups containing 8 to 60 ring atoms.

In a certain preferred embodiment, ar ¹ -Ar ⁴ Wherein at least two are selected from substituted or unsubstituted fused ring aromatic groups containing 10-30C atoms or fused ring heteroaromatic groups containing 8-30 ring atoms; in a certain preferred embodiment, ar ¹ Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms; in a certain preferred embodiment, ar ² Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms; in a certain preferred embodiment, ar ³ Selected from substituted or unsubstituted fused ring aromatic groups containing 10-30C atoms or fused ring heteroaromatic groups containing 8-30 ring atoms; in a certain preferred embodiment, ar ⁴ Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms.

In a certain preferred embodiment, ar ¹ And Ar ³ Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms; in a certain preferred embodiment, ar ¹ And Ar ⁴ Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms; in a certain preferred embodiment, ar ¹ And Ar ² Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 30C atoms or fused ring heteroaromatic groups containing 8 to 30 ring atoms.

In a certain preferred embodiment, the above-mentioned fused ring aromatic groups are selected from, but not limited to: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the fused ring heteroaromatic group is selected from the group consisting of benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primidine, quinazoline, quinazolinone, and derivatives thereof.

In a preferred embodiment, ar is ¹ -Ar ⁴ Each independently selected from the group consisting of:

wherein:

each occurrence of Y is independently represented by CR ₃ R ₄ 、NR ₃ 、O、S、SiR ₃ R ₄ 、PR ₃ 、P(＝O)R ₃ 、S＝O、S(＝O) ₂ Or C = O;

x independently represents CR at each occurrence ₃ Or N;

R ₃ and R ₄ Independently at each occurrence, is selected from H, D, or a straight chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms or a thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group ₃ Cl, br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

In one embodiment, each occurrence of Y is independently designated CR ₃ R ₄ 、NR ₃ O or S; x, at each occurrence, independently represents CR ₃ Or N;

R ₃ and R ₄ Each occurrence is independently selected from H, D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms.

Further, ar ¹ -Ar ⁴ Independently selected from the group consisting of:

in some of these embodiments, ar ¹ -Ar ⁴ Each independently selected from the group consisting of:

in one embodiment, ar ¹ -Ar ⁴ At least one of them is selected from

In some of these embodiments, ar ¹ -Ar ⁴ At least one of which is selected from substituted or unsubstituted naphthalene, benzene, pyridine, quinoxaline, isoquinoline, phenanthroline or phenanthrene. Further, ar ¹ -Ar ⁴ Are selected from substituted or unsubstituted naphthalene, benzene, pyridine, quinoxaline, isoquinoline, phenanthroline or phenanthrene.

In a certain preferred embodiment, ar ¹ -Ar ⁴ At least one of them is selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ¹ -Ar ⁴ At least two of which are selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ¹ Selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ² Selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ³ Selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ⁴ Selected from substituted or unsubstituted naphthalene orPhenanthrene; in a certain preferred embodiment, ar ¹ And Ar ³ Selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ¹ And Ar ⁴ Selected from substituted or unsubstituted naphthalene or phenanthrene; in a certain preferred embodiment, ar ¹ And Ar ² Selected from substituted or unsubstituted naphthalene or phenanthrene.

In a certain preferred embodiment, ar ¹ -Ar ⁴ At least three of which are selected from benzene; in a certain preferred embodiment, ar ¹ -Ar ⁴ All selected from benzene.

In a certain preferred embodiment, formula (1) is selected from any one of formulae (2-1) to (2-4):

in one embodiment, ar ¹ -Ar ⁴ Independently selected from substituted or unsubstituted aromatic groups containing 6 to 60C atoms or heteroaromatic groups containing 5 to 60 ring atoms;

x in the formulae (2-1) to (2-4) ₁ ～X ₃ Independently selected from CR ₁ R ₂ ，SiR ₁ R ₂ ，NR ₁ ，C(＝O)，S，S(＝O) ₂ Or O.

Further, the general formula (1) is selected from any one of formulae (3-1) to (3-27):

in a certain preferred embodiment, formula (1) is selected from any one of the following formulae:

in a certain preferred embodiment, X ₁ ～X ₃ Independently at each occurrence is selected from CR ₁ R ₂ 、NR ₁ S, or O; in a certain excellenceIn alternative embodiments, X ₁ ～X ₃ At least one selected from NR in each occurrence ₁ (ii) a In a certain preferred embodiment, X ₁ ～X ₃ When present, are all selected from NR ₁ 。

In a preferred embodiment, R ₁ At least one, when present, selected from electron withdrawing groups, preferably R ₁ When present, at least one structural unit selected from the group consisting of:

wherein:

W ¹ –W ⁸ at each occurrence, each independently represents CR ₅ Or N; preferably, W ¹ –W ⁸ At least one is selected from N;

Z ₁ -Z ₃ is a single bond or CR ₆ R ₇ Or O or S or none;

r is selected from any integer from 1 to 3;

R ₅ -R ₇ independently at each occurrence, is selected from H, D, or a straight chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms or a thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group ₃ A Cl, br, F, I crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

In a preferred embodiment, R ₁ At least one, when present, is selected from the group consisting of:

wherein: ar (Ar) ⁵ -Ar ⁶ Each independently selected from substituted or unsubstituted aromatic groups containing 6 to 60C atoms or heteroaromatic groups containing 5 to 60 ring atoms or non-aromatic ring systems containing 3 to 30 ring atoms.

In particular, at least one R ₁ Selected from the group consisting of:

* Is a linking site.

In a more preferred embodiment, the organic compound according to the present invention, formula (1) is selected from formula (4):

further, the general formula (4) is selected from the structures shown below:

wherein: r is ₁ The meaning is the same as above.

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

the compounds according to the invention can be used as functional materials in electronic devices, in particular in OLED devices. Organic functional materials may be classified into a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting material (Emitter), a Host material (Host), and an organic dye. In a preferred embodiment, the compounds according to the invention can be used as host materials, or electron-transport materials, or hole-transport materials.

In a preferred embodiment, the compounds according to the invention can be used as phosphorescent host materials or as co-host materials.

As a phosphorescent host material, it must have an appropriate triplet energy level, i.e., T ₁ . In certain embodiments, a compound according to the invention, T thereof ₁ More preferably, it is not less than 1.5eV, still more preferably not less than 1.6eV, still more preferably not less than 2.0eV, particularly preferably not less than 2.1eV.

Good thermal stability is desired as a phosphorescent host material. Generally, the compounds according to the invention have a glass transition temperature Tg of not less than 100 ℃, preferably not less than 140 ℃ and more preferably not less than 180 ℃.

In certain preferred embodiments, the compounds according to the invention, which ((HOMO- (HOMO-1)). Gtoreq.0.2 eV, preferably ≧ 0.3eV, more preferably ≧ 0.4eV, most preferably ≧ 0.45eV.

In further preferred embodiments, the compounds according to the invention (((LUMO + 1) -LUMO) are > 0.15eV, preferably > 0.25eV, more preferably > 0.30eV, most preferably > 0.35eV.

In some embodiments, the organic compounds according to the present invention have a light-emitting function with a light-emitting wavelength of between 300nm and 1000nm, preferably between 350nm and 900nm, and more preferably between 400nm and 800 nm. Luminescence as used herein refers to photoluminescence or electroluminescence.

In another preferred embodiment, the compounds according to the invention can be used as fluorescent host materials.

The invention also relates to a polymer comprising at least one repeating unit selected from any one of the organic compounds described above.

The invention also relates to a mixture comprising any one of the above organic compounds or any one of the above polymers and at least one organic functional material. The organic functional material comprises a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminous body or a main body material. The luminophores are selected from singlet state luminophores (fluorescent luminophores) and triplet state luminophores (phosphorescent luminophores) grade organic thermal excitation delayed fluorescence materials (TADF materials). Various organic functional materials are described in detail, for example, in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain embodiments, the mixture comprises at least one organic compound or polymer according to the invention and a fluorescent emitter. The compounds according to the invention can be used as fluorescent host materials in which the fluorescent emitters are present in an amount of <10% by weight, preferably < 9% by weight, more preferably < 8% by weight, particularly preferably < 7% by weight, most preferably < 5% by weight.

In a particularly preferred embodiment, the mixture comprises at least one organic compound or polymer according to the invention and a phosphorescent emitter. The compounds according to the invention can be used as phosphorescent host materials in which the phosphorescent emitters are present in amounts of < 25% by weight, preferably < 20% by weight, more preferably < 15% by weight.

In a further preferred embodiment, the mixture comprises at least one organic compound or polymer according to the invention, and a phosphorescent emitter and a further host material (triplet host material). In such an embodiment, the compounds according to the invention can be used as auxiliary luminescent materials in a weight ratio to phosphorescent emitter of from 1. In another preferred embodiment, the compound or polymer according to the invention forms an exciplex with another host material, said exciplex having an energy level higher than that of said phosphorescent emitter.

In another preferred embodiment, the mixture comprises at least one organic compound or polymer according to the invention and a TADF material. The compounds according to the invention can be used as host materials for TADF phosphors, wherein the TADF materials are present in an amount of 15 wt.% or less, preferably 10 wt.% or less, more preferably 8 wt.% or less.

In a very preferred embodiment, the mixture comprises one organic compound or polymer according to the invention and another host material (triplet host material). The organic compound according to the invention can be used here as a second body in a proportion of 30 to 70% by weight, preferably 40 to 60% by weight.

Details of the host materials, phosphorescent emitter materials, fluorescent emitter materials and TADF materials are described in WO2048095395.

It is an object of the present invention to provide a material solution for evaporation type OLEDs.

In certain embodiments, the compounds according to the invention have a molecular weight of 1100g/mol or less, preferably 1000g/mol or less, very preferably 950g/mol or less, more preferably 900g/mol or less, and most preferably 800g/mol or less.

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

In certain embodiments, the compounds according to the invention have a molecular weight of 700g/mol or more, preferably 900g/mol or more, preferably 1000g/mol or more, and most preferably 1100g/mol or more.

In other embodiments, the compounds according to the invention have a solubility in toluene of 10mg/ml or more, preferably 15mg/ml or more, most preferably 20mg/ml or more at 25 ℃.

The present invention further relates to a composition or ink comprising any one of the organic compounds or polymers according to the invention, and at least one organic solvent.

For the printing process, the viscosity of the ink, surface tension, is an important parameter. Suitable inks have surface tension parameters suitable for a particular substrate and a particular printing process.

In a preferred embodiment, the ink according to the invention has a surface tension in the range of about 19dyne/cm to about 50dyne/cm at operating temperature or at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.

In another preferred embodiment, the viscosity of the ink according to the invention ranges from about 1cps to about 100cps at operating temperature or 25 ℃; preferably in the range of 1cps to 50 cps; more preferably in the range of 1.5cps to 20 cps; preferably in the range of 4.0cps to 20 cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of the functional material in the ink. The inks according to the invention comprising the organometallic complexes or polymers described facilitate the adjustment of the printing inks to the appropriate range according to the printing process used. Generally, the composition according to the present invention comprises the functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, still more preferably ranging from 0.5% to 10% by weight, and most preferably ranging from 1% to 5% by weight.

In some embodiments, the ink according to the invention, the at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents, in particular aliphatic chain/ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

Examples of solvents suitable for the present invention are, but not limited to: aromatic or heteroaromatic-based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, 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, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-dimethylphenyl) pyridine, 1, 2-dimethylbenzyl) ethane, 2-diisopropylbenzene, and the like; ketone-based solvents 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, isophorone, 2,6, 8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethyl native ether, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether, octyl 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; ester solvent: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like.

Further, according to the ink of the present invention, said at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, phorone, 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 embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent 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, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

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 of the embodiments of the present invention may comprise from 0.01% to 20% by weight of the organic compound or polymer or mixture according to the present invention, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, most preferably from 0.25% to 5% by weight of the organic compound or mixture thereof.

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 a printing or coating production process.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Ink jet printing, jet printing and gravure 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, and the like, for adjusting viscosity, film forming properties, improving adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., see the Handbook of Print Media, techniques and Production Methods, by Helmut Kipphan, ISBN 3-540-67326-1.

Based on the above Organic compounds, the present invention also provides a use of the Organic compound or mixture or polymer or composition as described above, i.e. the Organic compound or mixture or polymer or composition is applied to an Organic electronic device, which can be selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light Emitting cells (OLEECs), organic Field Effect Transistors (OFETs), organic light Emitting field effect transistors (effets), organic lasers, organic spintronic devices, organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., and particularly preferred are Organic electroluminescent devices, such as OLEDs, OLEECs, organic light Emitting field effect transistors. In the embodiment of the present invention, the organic compound is preferably used for a light emitting layer of an electroluminescent device.

The invention also relates to the use of any one of the above organic compounds or polymers or mixtures or compositions for the preparation of electronic devices; further, in the preparation of organic electronic devices.

The invention further relates to an organic electronic device comprising at least one organic compound or polymer or mixture or composition as described above. Generally, such organic electronic devices comprise at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above. The Organic electronic device can be selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light Emitting cells (OLEECs), organic Field Effect Transistors (OFETs), organic light Emitting field effect transistors (effets), organic lasers, organic spintronic devices, organic sensors, organic Plasmon Emitting diodes (Organic plasma Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, organic light Emitting field effect transistors.

In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer comprising any one of the organic compounds or polymers or mixtures or compositions described above; or comprises any of the organic compounds described above and a phosphorescent emitter, or comprises any of the organic compounds described above and a host material, or comprises any of the organic compounds described above, a phosphorescent emitter and a host material.

An electroluminescent device as described above, in particular an OLED, 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 flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates free of surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ℃ or higher, preferably above 200 ℃, more preferably above 250 ℃, and most preferably above 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 an emission 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 the p-type semiconductor material acting as a 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 level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/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 also comprise further 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). Suitable materials for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In a preferred embodiment, the light-emitting device according to the invention is a light-emitting device in which the light-emitting layer is prepared from a composition according to the invention.

The light-emitting device according to the present invention emits light at a wavelength of 300nm to 1000nm, preferably 350nm to 900nm, more preferably 400nm to 800 nm.

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

The invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

While the present invention will be described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but rather it is intended that the appended claims cover all such modifications and variations as fall within the true spirit and scope of the invention.

Example 1

The synthetic route of compound (2) is as follows:

synthesis of intermediate 2-1:

under the protection of nitrogen, respectively adding 250 g of 2, 3-dinitro-1, 4-naphthalenediol (100 mmol) and 2.44 g of 4-Dimethylaminopyridine (DMAP) (20.0 mmol) into a dry three-neck flask, adding 1500ml of dichloromethane to dissolve the dichloromethane, cooling the reaction solution to 0 ℃, slowly dropwise adding 62ml (444 mmol) of Triethylamine (TEA), continuously stirring for 20min after dropwise adding is completed, continuously slowly dropwise adding 62.6 g of trifluoromethyl sulfonic anhydride (222 mmol) into the reaction solution at 0 ℃, continuously stirring for 1h after dropwise adding is completed, adding water to extract and kill the reaction until the reaction is completed, simultaneously extracting the organic phase by dichloromethane, combining and washing the organic phase for multiple times, drying by magnesium sulfate, filtering, rotatably evaporating to obtain a crude port, and purifying by fast column chromatography to obtain 440g of an intermediate 2-1, wherein the yield is as follows: 85.8 percent. MS (ASAP) =514.1.

Synthesis of intermediate 2-2

In a 500ml three-necked flask, 20g,100mmol of o-bromobenzoic acid, 25.7g,50mmol of intermediate 2-1, 6.9g,50mmol of sodium carbonate, 1.116g, and 1mmolPd (PPh) were charged ₃ ) ₄ 300ml of toluene, 75ml of water and 25ml of ethanol in N ₂ Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. The reaction solution was poured into water, washed to remove Na ₂ CO ₃ Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing the crude product by using dichloromethane and methanol to obtain 22.4g of an intermediate 2-2, wherein the yield is as follows: 85.2 percent. MS (ASAP) =526.4.

Synthesis of intermediates 2-3

A500 ml three-necked flask was charged with 22g,100mmol of pinacol o-aminobenzoate, 26.3g,50mmol of intermediate 2-2, 6.9g,50mmol of potassium carbonate, 1.16g, and 1mmol of Pd (PPh) ₃ ) ₄ 300ml of toluene, 75ml of water and 25ml of ethanol in N ₂ Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K ₂ CO ₃ Then, the solid product was obtained by suction filtration, and washed with dichloromethane. The crude product was recrystallized from dichloromethane and ethanol to give 21.5g of intermediate 2-3, yield: 77.8 percent. MS (ASAP) =552.6.

Synthesis of intermediates 2 to 4

55.3g of intermediate 2-3 was dissolved in a mixture of 250ml of acetic acid and 25ml of sulfuric acid in a 500ml three-necked flask, cooled to 0 ℃ and slowly dropped into the reaction mixture 16.0g of sodium nitrite, followed by stirring for 40min. After the reaction is completed, the reaction solution is dripped into water, the suspended crude product on the water surface is filtered, dried and purified by adopting rapid silica gel column chromatography to obtain 5g of an intermediate 2-4, and the yield is as follows: 9.6 percent. MS (ASAP) =518.2.

Synthesis of intermediates 2 to 5

Adding 51.8g of intermediate 2-4, 480ml of triethyl phosphate and 400ml of o-dichlorobenzene into a dry flask, heating and refluxing for 3 hours, extracting the reaction solution by using ethyl acetate after the reaction is completed, washing by using water for 3 times, combining organic phases, drying by using magnesium sulfate, filtering, and evaporating the solvent to obtain a crude product. Intermediate 2-5 was obtained by flash silica gel column chromatography with a mass of 34.5 g, yield: 76.0 percent. MS (ASAP) =454.5.

Synthesis of intermediates 2 to 6

Adding 45.5g of intermediate 2-5, 20.5g of iodobenzene, 13.8g of dried potassium carbonate powder and 500ml of o-dichlorobenzene into a dry three-neck flask, heating to 140 ℃ for reacting for 8 hours, extracting a reaction solution by using dichloromethane after the reaction is completed, washing 3 times by using water, combining organic phases, drying by using magnesium sulfate, filtering, and evaporating a solvent to dryness to obtain a crude product. Intermediate 2-6 was obtained by flash silica gel column chromatography with a mass of 45.4 g, yield: 85.7 percent. MS (ASAP) =530.4.

Synthesis of Compound (2)

Under the protection of nitrogen, 53.0 g of intermediate 2-6 (100 mmol) and 12.2 g of 4-Dimethylaminopyridine (DMAP) (100.0 mmol) are respectively added into a dry three-neck flask, 1500ml of tetrahydrofuran is added to dissolve the intermediate and the DMAP, the reaction solution is stirred for 30min to fully dissolve the intermediate and the DMAP, 24.0g of tetrahydrofuran solution of a compound 7 is slowly dripped, the mixture is continuously heated to 80 ℃ after the dripping is completed, the reaction is carried out for 4 hours, water is added to carry out extraction and quenching reaction after the reaction is completed, meanwhile, dichloromethane is used for extracting organic phases, the organic phases are combined and washed for multiple times, magnesium sulfate is used for drying, filtering is carried out, solvent is evaporated to obtain a crude port, and the crude port is purified by using a flash column chromatography to obtain a compound (2), the mass is 58.4g, and the yield: 79.5 percent. MS (ASAP) =734.1.

Example 2

The synthetic route of compound (11) is as follows:

synthesis of intermediate 11-2

A500 ml three-necked flask was charged with 22.0g,100mmol of pinacol o-aminobenzoate, 33.3g,50mmol of Compound 1-1, 6.9g,50mmol of Potassium carbonate, 1.16g, and 1mmol of Pd (PPh) ₃ ) ₄ 300ml of toluene, 75ml of water and 25ml of ethanol in N ₂ Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K ₂ CO ₃ Then, the solid product was obtained by suction filtration and washed with methylene chloride. The crude product was recrystallized from dichloromethane, ethanol to yield 24.3g of intermediate 11-2, yield: 70.8 percent. MS (ASAP) =686.6.

Synthesis of intermediate 11-3

68.6g of intermediate 11-2 was dissolved in a mixture of 250ml of acetic acid and 25ml of sulfuric acid in a 500ml three-necked flask, cooled to 0 ℃ and slowly dropped into the reaction mixture 16.0g of sodium nitrite, followed by stirring for 40min. After the reaction is completed, the reaction solution is dripped into water, the suspended crude product on the water surface is filtered, dried and purified by flash silica gel column chromatography to obtain 5.4g of an intermediate 11-3, and the yield is as follows: 8.3 percent. MS (ASAP) =651.7.

Synthesis of intermediate 11-4

Adding 51.8g of intermediate 11-3, 480ml of triethyl phosphate and 400ml of o-dichlorobenzene into a dry flask, heating and refluxing for 3 hours, extracting the reaction solution by using ethyl acetate after the reaction is completed, washing by using water for 3 times, combining organic phases, drying by using magnesium sulfate, filtering, and evaporating the solvent to obtain a crude product. Intermediate 11-4 was obtained by flash silica gel column chromatography with a mass of 47.5 g, yield: 76.0 percent. MS (ASAP) =618.5.

Synthesis of Compound (11)

Under the protection of nitrogen, 61.8 g of intermediate 11-4 (100 mmol), 26.8 g of 2, 4-diphenyl-6-chloro-1, 3, 5-triazine, 2.24 g of palladium acetate (1.0 mmol) and 13.8g of potassium carbonate are respectively added into a dry three-neck flask, 1500ml of tetrahydrofuran is added for dissolution, the mixture is heated to 80 ℃ until the reaction liquid refluxes, the reaction is carried out for 12 hours, after the reaction is completed, water is added for extraction and reaction, meanwhile, dichloromethane is used for extraction of organic phases, the organic phases are combined and washed for multiple times, magnesium sulfate is used for drying, filtration is carried out, the solvent is evaporated to dryness to obtain a coarse mouth, and flash column chromatography is used for purification to obtain 68.9g of compound (11), and the yield: 80.1 percent. MS (ASAP) =851.1.

Example 3

The synthetic route for compound (22) is as follows:

synthesis of intermediate 22-2:

the synthesis method is basically the same as that of the intermediate 2-3 in the compound (2), except that the dosage of the pinacol ester o-aminophenylboronic acid is halved, and the yield is as follows: 84.5 percent. MS (ASAP) =540.6.

Synthesis of intermediate 22-3:

method for the synthesis of intermediate 22-3 the synthesis of intermediate 22-2 was carried out by the classical SUZUKI reaction, except that pinacol ester of anthranilic acid was replaced by pinacol ester of 2-amino-3-naphthaleneboronic acid, with the following yields: 80.4 percent. MS (ASAP) =602.6.

Synthesis of intermediate 22-4:

synthetic methods reference was made to the synthetic methods of intermediates 2-4 in compound (2), yields: 8.5 percent. MS (ASAP) =568.6.

Synthesis of intermediate 22-5:

synthetic methods reference was made to the synthetic methods of intermediates 2-5 in compound (2), yields: 71.1 percent. MS (ASAP) =504.4.

Synthesis of intermediate 22-6:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 80.3 percent. MS (ASAP) =580.7.

Synthesis of Compound (22):

synthesis of compound (22) reference to the synthesis of compound (2), yield: 80.4 percent. MS (ASAP) =784.9.

Example 4

The synthetic route of compound (27) is as follows:

synthesis of intermediate 27-2:

synthesis methods reference the synthesis of intermediate 2-3 in compound (2), synthesized using the classical SUZUKI reaction, except that the amount of pinacol ester o-aminobenzeneboronic acid was halved, yield: 85.8 percent. MS (ASAP) =540.4.

Synthesis of intermediate 27-3:

method for synthesizing intermediate 27-3 referring to the method for synthesizing intermediate 27-2, the classical SUZUKI reaction is adopted for synthesis, wherein pinacol ester o-aminobenzeneboronic acid is replaced by pinacol ester 2-amino-3-naphthaleneboronic acid, and the yield is as follows: 85.4 percent. MS (ASAP) =602.8.

Synthesis of intermediate 27-4:

synthetic methods reference was made to the synthetic methods of intermediates 2-4 in compound (2), yields: 6.5 percent. MS (ASAP) =568.4.

Synthesis of intermediates 27-5:

synthetic methods reference was made to the synthetic methods of intermediates 2-5 in compound (2), yields: 65.4 percent. MS (ASAP) =504.4.

Synthesis of intermediates 27-6:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 85.3 percent. MS (ASAP) =580.4.

Synthesis of Compound (27):

synthesis method of Compound (27) with reference to the synthesis method of Compound (2), compound 2-7 was replaced with phenyl-substituted chloroquinoxaline (27-7), yield: 74.4 percent. MS (ASAP) =784.8.

Example 5

The synthetic route for compound (36) is as follows:

synthesis of intermediate 36-2:

synthesis method referring to the synthesis method of intermediate 2-3 in compound (2), the o-aminobenzeneboronic acid pinacol ester was replaced with 2-amino-3-naphthaleneboronic acid pinacol ester using the classical SUZUKI reaction synthesis, yield: 80.4 percent. MS (ASAP) =652.4.

Synthesis of intermediate 36-3:

synthesis method reference is made to the synthesis method of intermediates 2-4 in compound (2), yield: 8.9 percent. MS (ASAP) =618.8.

Synthesis of intermediate 36-4:

synthesis method reference is made to the synthesis method of intermediates 2-5 in compound (2), yield: and 69.4 percent. MS (ASAP) =554.6.

Synthesis of intermediate 36-5:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 89.4 percent. MS (ASAP) =630.7.

Synthesis of Compound (36):

synthesis of compound (36) reference is made to the synthesis of compound (11), yield: 79.8 percent. MS (ASAP) =862.0.

Example 6

The synthetic route for compound (107) is as follows:

synthesis of intermediate 107-2

Synthesis method referring to the synthesis method of intermediate 11-2 in compound (11), the classical SUZUKI reaction synthesis is adopted, the o-aminophenylboronic acid pinacol ester is replaced by 2-amino-3-naphthaleneboronic acid pinacol ester, and the input amount is halved, and the yield is: 75.4 percent. MS (ASAP) =723.4.

Synthesis of intermediate 107-3

Synthetic methods reference the synthetic method for intermediate 11-2 in compound (11), synthesized using the classical SUZUKI reaction, except substituting pinacol ester of ortho-aminophenylboronic acid with pinacol ester of 2-amino-3-naphthaleneboronic acid, yield: 84.4 percent. MS (ASAP) =735.8.

Synthesis of intermediate 107-4:

synthetic method reference was made to the synthetic method of intermediate 11-3 in compound (11), yield: 5.4 percent. MS (ASAP) =701.8.

Synthesis of intermediate 107-5:

synthetic method reference was made to the synthetic method of intermediate 11-4 in compound (11), yield: 78.1 percent. MS (ASAP) =669.8.

Synthesis of Compound (107)

Synthesis of compound (107) compound (11) was synthesized according to the classical Hartwig reaction, yield: 88.3 percent. MS (ASAP) =914.0.

Example 7

The synthetic route for compound (109) is as follows:

synthesis of intermediate 109-2:

synthetic method the synthesis was identical to that of intermediate 27-2 in reference compound (27), using the classical SUZUKI reaction, except that pinacol ester o-aminophenylboronic acid was changed to pinacol ester o-aminonaphthalene boronic acid, the amount used was doubled, the yield: 78.8 percent. MS (ASAP) =652.4.

Synthesis of intermediate 109-3:

synthetic methods reference was made to the synthetic methods of intermediates 2-4 in compound (2), yields: 5.8 percent. MS (ASAP) =618.4.

Synthesis of intermediate 109-4:

synthetic method and synthetic method of intermediates 2 to 5 in compound (2), yield: 67.6 percent. MS (ASAP) =554.4.

Synthesis of intermediate 109-5:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 87.8 percent. MS (ASAP) =630.7.

Synthesis of compound (109):

synthesis of compound (109) reference was made to the synthesis of compound (11) using the classical Hartwig reaction, yield: 85.5 percent. MS (ASAP) =875.0.

Example 8

The synthetic route for compound (125) is as follows:

synthesis of intermediate 125-2

Synthesis method referring to the synthesis method of intermediate 11-2 in compound (11), the synthesis was performed using the classical SUZUKI reaction except that pinacol ester ortho-aminobenzeneboronic acid was changed to pinacol ester 9-amino-10-phenanthreneboronic acid, and the input was halved, yield: 76.5 percent. MS (ASAP) =823.8.

Synthesis of intermediate 125-3

Synthesis method reference was made to the synthesis method of intermediate 11-2 in compound (11), using the classical SUZUKI reaction, in which pinacol ester o-aminophenylboronic acid was halved in amount and in yield: 85.6 percent. MS (ASAP) =836.1.

Synthesis of intermediate 125-4:

synthetic method reference was made to the synthetic method of intermediate 11-3 in compound (11), yield: 4.4 percent. MS (ASAP) =801.8.

Synthesis of intermediate 125-5:

synthetic method reference was made to the synthetic method of intermediate 11-4 in compound (11), yield: 88.4 percent. MS (ASAP) =768.8.

Synthesis of compound (125):

synthesis of compound (125) compound (11) was synthesized according to the classical Hartwig reaction, yield: 84.4 percent. MS (ASAP) =950.1.

Example 9

The synthetic route for compound (200) is as follows:

synthesis of intermediate 200-2:

synthesis method referring to the synthesis method of intermediate 27-2 in compound (27), the amount of pinacol ester ortho-aminophenylboronic acid was doubled by using the classical SUZUKI reaction synthesis, yield: 80.2 percent. MS (ASAP) =552.6.

Synthesis of intermediate 200-3:

synthesis method reference is made to the synthesis method of intermediates 2-4 in compound (2), yield: 4.6 percent. MS (ASAP) =518.5.

Synthesis of intermediate 200-4:

synthetic methods reference was made to the synthetic methods of intermediates 2-5 in compound (2), yields: 71.2 percent. MS (ASAP) =454.3.

Synthesis of intermediate 200-5:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 88.4 percent. MS (ASAP) =529.7.

Synthesis of Compound (200):

synthesis of compound (200) compound (11) was synthesized according to the classical Hartwig reaction, yield: 84.7 percent. MS (ASAP) =760.9.

Example 10

The synthetic route for compound (220) is as follows:

synthesis of intermediate 220-2:

synthesis method referring to the synthesis method of intermediate 27-2 in compound (27), synthesized using the classical SUZUKI reaction, the substitution of pinacol ester o-aminobenzeneboronic acid to pinacol ester 2-amino-3-naphthaleneboronic acid, yield: 79.1 percent. MS (ASAP) =640.5.

Synthesis of intermediate 3:

method of synthesis of intermediate 220-3 the synthesis was performed using the classical SUZUKI reaction, with reference to the synthesis of intermediate 220-2, except that the 2-amino-3-naphthaleneboronic acid pinacol ester was replaced with anthranilic acid pinacol ester, yield: 88.1 percent. MS (ASAP) =652.8.

Synthesis of intermediate 220-4:

synthesis method reference is made to the synthesis method of intermediates 2-4 in compound (2), yield: 4.8 percent. MS (ASAP) =618.4.

Synthesis of intermediate 220-5:

synthesis method reference is made to the synthesis method of intermediates 2-5 in compound (2), yield: 80.4 percent. MS (ASAP) =554.4.

Synthesis of intermediate 220-6:

synthetic methods reference was made to the synthetic methods of intermediates 2-6 in compound (2), yields: 84.5 percent. MS (ASAP) =629.7.

Synthesis of compound (220):

synthesis of compound (220) reference is made to the synthesis of compound (2), yield: 80.1 percent. MS (ASAP) =834.8.

Example 11

The synthetic route of compound (241) is as follows:

synthesis of intermediate 241-2

Synthetic methods reference the synthetic method for intermediate 11-2 in compound (11), synthesized using the classical SUZUKI reaction, yield: 80.4 percent. MS (ASAP) =537.6.

Synthesis of intermediate 241-3:

synthetic method reference was made to the synthetic method of intermediate 11-3 in compound (11), yield: 6.5 percent. MS (ASAP) =503.4.

Synthesis of intermediate 241-4:

synthetic method reference was made to the synthetic method of intermediate 11-4 in compound (11), yield: 84.6 percent. MS (ASAP) =470.5.

Synthesis of compound (241):

synthesis of compound (241) reference is made to the synthesis of compound (2), yield: 68.9 percent. MS (ASAP) =751.9.

Example 12

The synthetic route for compound (246) is as follows:

synthesis of intermediate 246-2

Synthetic methods reference the synthetic method for intermediate 11-2 in compound (11), synthesized using the classical SUZUKI reaction, yield: 79.7 percent. MS (ASAP) =521.5.

Synthesis of intermediate 246-3:

synthetic method reference was made to the synthetic method of intermediate 11-3 in compound (11), yield: 5.5 percent. MS (ASAP) =487.5.

Synthesis of intermediate 246-4:

synthetic method reference was made to the synthetic method of intermediate 11-4 in compound (11), yield: 76.8 percent. MS (ASAP) =454.5.

Synthesis of compound (246):

synthesis of compound (246) reference is made to the synthesis of compound (2), yield: 74.1 percent. MS (ASAP) =735.6.

Example 13

The synthetic route for compound (262) is as follows:

synthesis of intermediate 262-2:

synthesis method reference was made to the synthesis of intermediate 27-2 in compound (27), synthesized using the classical SUZUKI reaction, yield: 84.1 percent. MS (ASAP) =553.5.

Synthesis of intermediate 262-3:

synthesis of intermediate 262-3 the synthesis was performed using the classical SUZUKI reaction, referring to the synthesis of intermediate 262-2, except substituting pinacol o-aminophenylborate for pinacol 9-amino-10 phenanthreneborate, yield: 84.5 percent. MS (ASAP) =665.8.

Synthesis of intermediate 262-4:

synthetic methods reference was made to the synthetic methods of intermediates 2-4 in compound (2), yields: 5.1 percent. MS (ASAP) =631.8.

Synthesis of intermediate 262-5:

adding 63.1g of intermediate 262-4 into a dry flask, adding THF at room temperature to completely stir and dissolve, cooling the temperature of a reaction solution to 0 ℃ in an ice bath, slowly dropping 200mmol of methyl magnesium bromide Grignard reagent under the protection of nitrogen, continuing stirring at room temperature for 1 hour after dropping is finished, adding water to quench the reaction, extracting the obtained mixed reaction solution with dichloromethane for 3 times, combining organic phases, drying with magnesium sulfate, filtering, evaporating the solvent to dryness to obtain a crude product, recrystallizing with dichloromethane and methanol to obtain an intermediate product, wherein the yield is as follows: 58.9%, MS (ASAP) =631.7. And directly putting the obtained intermediate product into the next reaction, dissolving the intermediate product into THF, heating to a reflux state, dropwise adding concentrated hydrochloric acid for reaction, continuously heating for reaction for 1 hour after dropwise adding of the concentrated hydrochloric acid is finished, tracking the reaction by TLC, cooling to room temperature after the reaction is completed, adding alkaline solution to neutralize unreacted hydrochloric acid, filtering to obtain a crude product, and recrystallizing to obtain an intermediate 262-5 with yield: 75.4%, MS (ASAP) =613.7.

Synthesis of intermediate 262-6:

synthesis method reference is made to the synthesis method of intermediates 2-5 in compound (2), yield: 82.4 percent. MS (ASAP) =581.7.

Synthesis of compound (262):

synthesis of compound (262) compound (11) was synthesized according to the classical Hartwig reaction, yield: 81.1 percent. MS (ASAP) =765.9.

Example 14

The synthetic route for compound (266) is as follows:

synthesis of intermediate 266-2:

synthetic methods reference the synthetic method for intermediate 27-2 in compound (27), synthesized using the classical SUZUKI reaction, yield: 80.7 percent. MS (ASAP) =552.4.

Synthesis of intermediate 266-3:

synthesis of intermediate 266-3 reference was made to the synthesis of intermediate 266-2, which was synthesized using the classical SUZUKI reaction, yield: 74.6 percent. MS (ASAP) =617.6.

Synthesis of intermediate 266-4:

synthesis method reference is made to the synthesis method of intermediates 2-4 in compound (2), yield: 4.3 percent. MS (ASAP) =583.8.

Synthesis of intermediate 266-5:

synthesis method reference is made to the synthesis of intermediate 262-5 in compound (262), yield: 40.1%, MS (ASAP) =565.6.

Synthesis of intermediate 266-6:

synthesis method reference is made to the synthesis method of intermediates 2-5 in compound (2), yield: 80.2 percent. MS (ASAP) =533.7.

Synthesis of Compound (266):

synthesis of compound (266) compound (11) was synthesized using the classical Hartwig reaction, yield: 78.1 percent. MS (ASAP) =764.9.

Comparative example

The synthesis procedure of the REF material is described in the following documents: WO2018159964A1.

Preparing an OLED device:

the device structure is as follows: ITO/NPD (35 nm)/Compound (2): 10% (btp) ₂ The preparation steps of an Ir (acac) (40 nm)/TPBi (65 nm)/LiF (1 nm)/Al (150 nm) OLED device are as follows:

HTL materials: NPD EML material: compound (2): 10% (btp) ₂ Ir (acac) ETL material: TPBi

a. Cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. HTL (35 nm), EML (40 nm), ETL (65 nm): under high vacuum (1X 10) ^-6 Mbar, mbar) through thermal evaporation;

c. cathode-LiF/Al (1 nm/150 nm) in high vacuum (1X 10) ^-6 Millibar) hot evaporation;

d. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

OLED 1: the host material of the luminescent layer of the organic electroluminescent device is the compound (2).

And an OLED 2: the host material of the light-emitting layer of the organic electroluminescent device is a compound (11).

And 3, OLED: the host material of the light-emitting layer of the organic electroluminescent device is a compound (22).

And an OLED 4: the host material of the light-emitting layer of the organic electroluminescent device is a compound (27).

And an OLED 5: the host material of the light-emitting layer of the organic electroluminescent device is a compound (36).

An OLED 6: the host material of the light-emitting layer of the organic electroluminescent device is a compound (107).

And an OLED (7): the host material of the light-emitting layer of the organic electroluminescent device is a compound (109).

And (3) OLED 8: the host material of the light-emitting layer of the organic electroluminescent device is a compound (125).

An OLED 9: the host material of the light-emitting layer of the organic electroluminescent device is a compound (200).

An OLED 10: the host material of the light-emitting layer of the organic electroluminescent device is a compound (220).

An OLED 11: the main material of the luminescent layer of the organic electroluminescent device is a compound (241).

The OLED 12: the host material of the light-emitting layer of the organic electroluminescent device is a compound (246).

The OLED 13: the host material of the light-emitting layer of the organic electroluminescent device is a compound (262).

The OLED 14: the host material of the light-emitting layer of the organic electroluminescent device is a compound (266).

OLED Ref: the main material of the light-emitting layer of the organic electroluminescent device is REF.

The current-voltage (J-V) characteristics of each OLED device were characterized by characterization equipment, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. As shown in table 1:

TABLE 1

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. As can be seen from the test data in Table 1, the red OLED device prepared by using the host material of the invention has greatly improved luminous efficiency and service life, and the external quantum efficiency is also obviously improved.

It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

Claims

1. An organic compound represented by the general formula (1):

wherein:

Ar ¹ -Ar ⁴ each independently selected from the group consisting of:

X ₁ ～X ₃ at each occurrence, is independently selected from none, or CR ₁ R ₂ ，NR ₁ Any one of S and O; wherein X ₁ ～X ₃ At most one is selected from the group consisting of none, at least one is selected from the group consisting of NR ₁ ；

R ₁ -R ₂ Each occurrence is independently selected from H, D, or a linear alkyl group having 1 to 20C atoms, or an alkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms;

and R is ₁ At least one, when present, is selected from the group consisting of:

* Is a linking site;

wherein "substituted or unsubstituted" means that the defined group is substituted or unsubstituted, and when substituted, the substituent is selected from: c ₁ - ₃₀ Alkyl, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, cyano, isocyano, hydroxy, trifluoromethyl, nitro or halogen.

2. The organic compound of claim 1, wherein Ar is Ar ¹ -Ar ⁴ Independently selected from naphthyl, phenyl, pyridyl, quinoxalinyl, isoquinolinyl, phenanthrolinyl or phenanthrenyl.

3. The organic compound according to claim 1, wherein the general formula (1) is selected from any one of formulae (2-1) to (2-4):

wherein:

Ar ¹ -Ar ⁴ 、X ₁ ～X ₃ the meaning of (A) is as defined in claim 1.

4. The organic compound according to claim 3, wherein the general formula (1) is selected from any one of formulae (3-1) to (3-27):

5. an organic compound according to claim 1, characterized in that: the general formula (1) is selected from formula (4):

6. an organic compound according to claim 1, characterized in that: the general formula (1) is selected from any one of the following structures:

7. a mixture comprising an organic compound according to any one of claims 1 to 6, and at least one organic functional material selected from a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material or a host material.

8. A composition comprising an organic compound according to any one of claims 1 to 6 or a mixture according to claim 7, and at least one organic solvent.

9. An organic electronic device comprising at least one organic compound according to any one of claims 1 to 6 or a mixture according to claim 7 or a composition according to claim 8.

10. The organic electronic device according to claim 9, wherein the organic electronic device comprises a light-emitting layer comprising the organic compound or the mixture or the composition.