CN112979678B - Organic compound, high polymer, mixture, composition and organic electronic device - Google Patents

Abstract

The invention discloses an N-containing condensed ring compound which has a structure shown as a general formula (1). The compounds according to the invention enhance the stability of the compounds by fusing together a plurality of aromatic groups through a seven-membered ring. The compound can be used as a main material to be applied to electroluminescent devices, particularly OLED devices. The compounds according to the invention can improve the luminous efficiency and the lifetime of electroluminescent devices by complexing with suitable guests, in particular phosphorescent guests or TADF emitters, and provide a solution for efficient, long-lived, low roll-off luminescent devices.

Description

Organic compound, high polymer, mixture, composition and organic electronic device

This application claims priority from the chinese patent application entitled "an organic compound, polymer, blend and use" filed by the chinese patent office on 16.12.2019 and having application number 201911290039.0, 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 containing N condensed rings, a high polymer, a mixture, a composition and an organic electronic device containing the organic compound.

Background

The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

In order to improve the light emitting efficiency of the organic light emitting diode, various phosphor-based and phosphorescent light emitting material systems have been developed, and the organic light emitting diode using a fluorescent material has a high reliability but has its internal electroluminescence quantum efficiency limited to 25% under electrical excitation because the ratio of the singlet excited state and the triplet excited state of current-generated excitons is 1:3. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency, and thus the development of the phosphorescent material 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. Since the host material greatly affects the efficiency and characteristics of the electroluminescent device when the host material/guest system is used as the light emitting layer of the light emitting device, the selection of the host material is important.

Currently, 4,4' -dicarbazole-biphenyl (CBP) is known to be the most widely used host material for phosphorescent materials. In recent years, pioneer corporation (Pioneer) and the like have developed a high-performance organic electroluminescent device using a compound such as BAlq (bis (2-methyl) -8-hydroxyquinolinato-4-phenylphenolaluminum (III)), phenanthroline (BCP), and the like as a substrate.

In the existing material design, people tend to adopt a combination containing an electron transport group and a hole transport group, and the combination is designed into a bipolar transport body, which is beneficial to the balance of charge transport, such as the triazine or pyrimidine derivatives disclosed in patents of US2016329506, US20170170409 and the like, or CN 104541576A. The bipolar transmission molecules are used as main bodies, so that good device performance can be obtained. The performance and lifetime of the resulting devices remain to be improved.

Thus, there is a need for improvements and developments in the art, particularly in the host material solutions.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a class of N-containing condensed ring organic compounds, high polymers, mixtures, compositions and organic electronic devices thereof, and aims to provide a class of novel host materials, and improve the stability and the service life of the devices.

The technical scheme of the invention is as follows:

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

wherein:

Ar ¹ -Ar ³ each independently selected from any one of the general formulae (A-1) to (A-7):

x is independently selected from CR at each occurrence ¹ Or N;

each occurrence of Y is independently selected from CR ² R ³ O or S;

Y ₁ 、Y ₂ independently selected from single bond, NR ⁴ 、CR ⁴ R ⁵ 、SiR ⁴ R ⁵ 、O、S、S(＝O) ₂ Or S (= O), Y ₁ 、Y ₂ Not simultaneously selected from single bonds;

when Ar is ¹ -Ar ³ When all are selected from (A-1), at least one X is selected from CR ¹ And at least one R ¹ Selected from any one of the structures of the general formulae (B-1) to (B-3):

X ₁ each occurrence is independently selected from CR ⁶ Or N;

Y ₃ independently selected from NR ⁷ 、CR ⁷ R ⁸ 、SiR ⁷ R ⁸ 、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 ¹ -R ⁸ each independently selected from H, D, a straight chain alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a 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 (- = O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, 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 radicals R ¹ -R ⁸ Aliphatic or aromatic rings which can form a single ring or multiple rings with each other and/or with the rings bonded to the radicals;

* Indicates the attachment site.

A high 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 organic compounds and the above high polymers, 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, an emitter, and a host material.

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

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

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

the organic compounds according to the invention can be used as host materials which, by complexing with suitable guests, in particular phosphorescent guests or TADF emitters, increase the lifetime of the electroluminescent device. Meanwhile, the solution of the light-emitting device with high efficiency and low roll-off is provided. In addition, the organic electroluminescent device is matched with another body with hole transport property or bipolar property to form a common body, so that the electroluminescent efficiency and the service life of the device can be further improved.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description. 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

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

In the present invention, the Host material, the matrix material and the Host material have the same meaning and may be interchanged. In the embodiments of the present invention, the singlet state and the singlet state have the same meaning and may be interchanged with each other.

In the embodiments of the present invention, the triplet state and the triplet state have the same meaning and may be interchanged.

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 to be optionally 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, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused ring aromatic systems for the purposes of this invention.

Specifically, examples of the condensed ring aromatic group are: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

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

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

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

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

In the present invention, "-" attached to a single bond indicates a connection site; in the context of the present invention, when no attachment site is indicated, the expression optional attachable position on the respective group is used as an attachment site, the single bond to which the substituent is attached extends through the respective ring, and the expression substituent is used to attach to an optional position on the ring, for example

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

In, Y ₁ And Y ₂ Can be attached to any adjacent X, and when attached to X, X is selected from C; in particular, the amount of the solvent to be used,

Included

and

two structures.

In the embodiment of the present invention, the energy level structures of the organic material, i.e., the triplet energy level ET1, the highest occupied orbital energy level HOMO, and the lowest unoccupied orbital energy level LUMO play a key role. The determination of these energy levels is 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.

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), as obtained by commercial software Gaussian09W (Gaussian inc.), the specific simulation method can be found in WO2011141110 or as described in the examples below.

It should be noted that HOMO, LUMO, ET ₁ The absolute value of (a) depends on the measurement method or calculation method used, and even in the case where the measurement method is the same and the evaluation method is different, different values can be given, for example, the starting point and the 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, ET ₁ 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 as a general formula (1):

wherein:

Ar ¹ -Ar ³ each independently selected from any one of the general formulae (A-1) to (A-7):

x is independently selected from CR for each occurrence ¹ Or N; preferably, X is independently selected from CR ¹ ；

Y is selected from CR ² R ³ O or S; preferably, Y is selected from O or S;

Y ₁ 、Y ₂ independently selected from single bond, NR ⁴ 、CR ⁴ R ⁵ 、SiR ⁴ R ⁵ 、O、S、S(＝O) ₂ Or S (= O), Y ₁ 、Y ₂ Is not simultaneously selected from single bonds;

when Ar is ¹ -Ar ³ When all are selected from (A-1), at least one X is selected from CR ¹ And at least one R ¹ Selected from any one of the structures of the general formulae (B-1) to (B-3):

X ₁ each occurrence is independently selected from CR ⁶ Or N; preferably, at least one X ₁ Is selected from N; in one embodiment, at least two X ₁ Is selected from N;

Y ₃ independently selected from NR ⁷ 、CR ⁷ R ⁸ 、SiR ⁷ R ⁸ 、O、S、S(＝O) ₂ Or S (= O);

l is selected from a single bond 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 ¹ -R ⁸ each independently selected from H, D, a straight chain alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a 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 (- = O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate groupHydroxy group, nitro group, 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 radicals R ¹ -R ⁸ The rings which may be bonded to each other and/or to the radicals form mono-or polycyclic aliphatic or aromatic rings.

In one embodiment, ar ¹ -Ar ³ Each independently selected from the group consisting of:

wherein: the H atom of the ring may be further substituted by R ¹ And (4) substitution.

In one embodiment, ar ¹ -Ar ³ Are all selected from (A-1), i.e. formula (1) is selected from formula (2):

wherein:

x is independently selected from CR ¹ ；

R ¹ When multiple occurrences, independently selected from H or general formulas (B-1) - (B-3);

the general formulas (B-1) to (B-3) are independently selected from any one of the structures of the general formulas (C-1) to (C-4):

in one embodiment, X in formula (2) occurs multiple times and there is one and only one R ¹ Selected from any one of the structures of the general formulas (C-1) to (C-4).

In one embodiment, X in the general formulae (C-1) to (C-4) ₁ Selected from the group consisting of CR ⁶ (ii) a More preferably, X ₁ Is selected from CH.

In one embodiment, R in the general formulae (C-1) to (C-4) ⁶ Selected from substituted orUnsubstituted aromatic or heteroaromatic groups having 6 to 15 ring atoms; more preferably, R ⁶ Selected from benzene or naphthalene or biphenyl.

In one embodiment, formula (1) is selected from the following formulas:

wherein: r ¹ Selected from any one of the structures of the general formulas (B-1) to (B-3); more preferably, R ¹ Selected from any one of the structures of the general formulas (C-1) to (C-4).

Further, the formula (1) is selected from the following formulas:

in one embodiment, ar ¹ -Ar ³ At least one structure selected from any one of the general formulas (A-2) to (A-7); preferably, ar ¹ -Ar ³ At least one selected from the general formula (A-2), (A-3), (A-4) or (A-7). In one embodiment, ar ¹ -Ar ³ At least one selected from the general formula (A-3).

In one embodiment, ar ¹ -Ar ³ At least one structure selected from any one of the general formulas (A-2) to (A-7) and at least one structure selected from the general formula (A-1); preferably, ar ¹ -Ar ³ At least one selected from the general formula (A-2), (A-3), (A-4) or (A-7) and at least one selected from the general formula (A-1).

In one embodiment, ar ¹ -Ar ³ At least one selected from the general formula (A-3) and at least one selected from the general formula (A-1).

In one embodiment, ar ¹ -Ar ³ One of them is selected from the general formula (A-2), (A-3), (A-4) or (A-7), and the other two are selected from the general formula (A-1).

In one embodiment, ar ¹ -Ar ³ Two of them are selected from the general formula (A-2), (A-3) or (A-4), and one is selected from the general formula (A-1). In one embodiment, according to the inventionOrganic compounds of formula (I), ar ¹ -Ar ³ At least one structure selected from (A-2) to (A-7), and the organic compound at least comprises one structure selected from (B-1) to (B-3); preferably, ar ¹ -Ar ³ At least one structure selected from any one of general formulas (A-2) to (A-4), and the organic compound at least comprises any one structure selected from general formulas (B-1) to (B-3).

The expression "the organic compound contains at least one structure of any one of the general formulae (B-1) to (B-3)" means:

in the general formula (1) if Ar ¹ -Ar ³ Selected from the general formula (A-2) or (A-4) - (A-6), then at least one X is selected from CR ¹ (ii) a And at least one R ¹ Selected from any one of the general formulas (B-1) to (B-3).

If Ar in the general formula (1) ¹ -Ar ³ At least one selected from the general formulae (A-3) or (A-7), then X, Y ₁ And Y ₂ Substituent (R) ¹ 、R ⁴ 、R ⁵ ) At least one of them is selected from any one of the structures of the general formulas (B-1) to (B-3).

The same is true for the phrase "the organic compound contains at least one structure of any one of the general formulae (C-1) to (C-4)".

Further, the general formula (1) is selected from any one of the structures of the general formulae (3-1) to (3-13):

in a preferred embodiment, X is selected from CR ¹ (ii) a More preferably, R ¹ When multiple occurrences, it is independently selected from H or general formulas (B-1) to (B-3).

In a preferred embodiment, Y in the general formulae (3-1) to (3-6) ₁ 、Y ₂ One of which is selected from single bonds. More preferably, the other is selected from NR ⁴ 、CR ⁴ R ⁵ 、O、S。

In one embodiment, Y in the general formulae (3-1) to (3-6) ₁ 、Y ₂ One of them is selected from single bond and the other is selected from NR ⁴ (ii) a Preferably R ⁴ Selected from any one of the structures of the general formulas (B-1) to (B-3); more preferably, R ⁴ Selected from any one of the structures of the general formulas (C-1) to (C-4).

In one embodiment, Y in the general formulae (3-1) to (3-6) ₁ 、Y ₂ One of them is selected from single bond and the other is selected from CR ⁴ R ⁵ O or S; at least one X in the general formulae (3-1) to (3-6) is selected from CR ¹ (ii) a And at least one R ¹ Selected from any one of the general formulas (B-1) to (B-3).

In one embodiment, formula (1) is selected from any one of formulae (4-1) to (4-9):

preferably, R in the general formulae (4-1) to (4-4) and (4-13) ⁴ Selected from any one of the structures of the general formulas (B-1) to (B-3); more preferably, R ⁴ Selected from any one of the structures of the general formulas (C-1) to (C-4).

Preferably, R in the general formulae (4-5) to (4-12) ¹ Selected from any one of the structures of the general formulas (B-1) to (B-3); more preferably, R ¹ Selected from any one of the structures of the general formulas (C-1) to (C-4); more preferably, Y ₁ Selected from the group consisting of CR ⁴ R ⁵ O or S.

In one embodiment, the organic compound according to the invention, the organic compound comprising at least one R ¹ Or R ⁴ And at least one R ¹ Or R ⁴ Selected from any one of the structures of the general formulae (B-1) to (B-3):

more preferably, according to the organic compound of the present invention, the organic compound contains at least one R ¹ Or R ⁴ And at least one R ¹ Or R ⁴ Selected from any one of the structures of the general formulae (C-1) to (C-4):

in one embodiment, theX in the formulae (C-1) to (C-4) ₁ Selected from the group consisting of CR ⁶ (ii) a More preferably, X ₁ Is selected from CH.

In one embodiment, R in the general formulae (C-1) to (C-4) ⁶ Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 15 ring atoms; more preferably, R ⁶ Selected from benzene or naphthalene or biphenyl.

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 substituted or unsubstituted aromatic groups having 6 to 15 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 15 ring atoms.

In one embodiment, L ₁ Selected from the group consisting of:

wherein: x ₁ ，Y ₃ The meaning is the same as above.

Further, L ₁ Selected from single bonds or the following groups:

the organic compounds according to the invention are preferably selected from, but not limited to, the following structures:

wherein: the H atoms 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 material includes, but is not limited to, 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), an Emitter (Emitter), and a Host material (Host).

In a particularly preferred embodiment, the organic compounds according to the invention are used as host materials, in particular phosphorescent host materials.

As a phosphorescent host material, it must have an appropriate triplet energy level, E _T1 . In certain embodiments, N-containing fused ring compounds, E thereof, according to the invention _T1 Not less than 2.2eV; more preferably at least 2.4eV, still more preferably at least 2.6eV.

In a preferred embodiment, the organic compound according to the present invention has a suitable resonance factor f (S1), which facilitates the transfer of excitons from the host to the guest, and improves the light-emitting efficiency of the device. Preferably, f (S1) ≥ 0.01, more preferably f (S1) ≥ 0.05, most preferably f (S1) ≥ 0.08.

In a further preferred embodiment, the organic compounds according to the invention have a more suitable singlet-triplet energy level difference Δ E _ST Thereby facilitating the transfer of excitons from the host to the guest and improving the luminous efficiency of the device. Preferably,. DELTA.E _ST Less than or equal to 0.9eV, preferably Delta E _ST 0.6eV or less, preferably,. DELTA.E _ST ≤0.4eV。

The organic compounds according to the invention have suitable Δ HOMO and Δ LUMO as host materials.

In certain preferred embodiments, the organic compound Δ HOMO according to the present invention, i.e., ((HOMO- (HOMO-1)) is preferably ≧ 0.1eV, more preferably ≧ 0.25eV, and most preferably ≧ 0.40eV.

In certain preferred embodiments, the organic compounds according to the present invention,. DELTA.LUMO (((LUMO + 1) -LUMO), is preferably ≧ 0.10eV, more preferably ≧ 0.20eV, and most preferably ≧ 0.30eV.

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

The present invention still 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-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-, and ULLMAN.

In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100 ℃ or higher, preferably 120 ℃ or higher, more preferably 140 ℃ or higher, more preferably 160 ℃ or higher, most preferably 180 ℃ or higher.

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

In a preferred embodiment, the polymers according to the invention preferably have a weight average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The invention also relates to a mixture comprising an organic functional material H1, the organic functional material H1 is selected from the organic compounds or high polymers mentioned above, and at least another organic functional material H2. The organic functional material H2 is selected from 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), an illuminant (Emitter) and a Host material (Host). The light-emitting material is selected from singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), in particular light-emitting organometallic complexes and organic thermally excited delayed fluorescence materials (TADF materials). Various organic functional materials are described in detail, for example, in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain preferred embodiments, the organic mixtures according to the invention wherein at least one of the organic functional materials H1 and H2 has a Δ LUMO ≧ 0.1eV, preferably ≧ 0.2eV, more preferably ≧ 0.2eV.

In a more preferred embodiment, the organic mixture according to the invention wherein the organic functional material H1 has a Δ LUMO ≧ 0.1eV, preferably ≧ 0.2eV, more preferably ≧ 0.3eV.

In certain preferred embodiments, the organic mixtures according to the invention wherein at least one of the organic functional materials H1 and H2 has a Δ HOMO ≧ 0.1eV, preferably ≧ 0.25eV, more preferably ≧ 0.4eV.

In a more preferred embodiment, the organic mixture according to the invention wherein the organic functional material H2 has a. DELTA. HOMO ≧ 0.1eV, preferably ≧ 0.25eV, more preferably ≧ 0.4eV.

In certain preferred embodiments, the organic mixture is described wherein min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)) +0.1eV, wherein LUMO (H1), HOMO (H1), and ET (H1) are the lowest unoccupied orbital, highest occupied orbital, and triplet energy levels of the organic functional material H1, respectively, and LUMO (H2), HOMO (H2), and HOME (H2) are the lowest unoccupied orbital, highest occupied orbital, and triplet energy levels of the organic functional material H2, respectively, more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)); still more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1)), (H2) _T (H1))，E _T (H2))-0.1eV。

In certain more preferred embodiments, the organic mixture 1) has a Δ E (S1-T1) of 0.60eV or less, preferably 0.44eV or less, more preferably 0.37eV or less, and most preferably 0.10eV or less for the organic functional material H1, and/or 2) has a LUMO of the organic functional material H2 higher than that of the organic functional material H1, and a HOMO of the organic functional material H2 lower than that of the organic functional material H1.

In a preferred embodiment, the organic mixture wherein the molar ratio of organic functional material H1 to H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; more preferred molar ratios are 4:6 to 6:4; the most preferred molar ratio is 4.5 to 5.5.

In a preferred embodiment, the organic mixture is one in which the difference between the molecular weights of the organic functional materials H1 and H2 is not more than 100Dalton, preferably not more than 80Dalton, more preferably not more than 70Dalton, still more preferably not more than 60Dalton, most preferably not more than 40Dalton, most preferably not more than 30Dalton.

In another preferred embodiment, the organic mixture wherein the difference between the sublimation temperatures of the organic functional materials H1 and H2 does not exceed 50K; more preferably the difference in sublimation temperatures 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, the organic functional materials H1 and H2 in the organic mixture according to the invention have at least one glass transition temperature Tg of 100 ℃ or higher, in a preferred embodiment at least one Tg of 120 ℃ or higher, in a more preferred embodiment at least one Tg of 140 ℃ or higher, in a more preferred embodiment at least one Tg of 160 ℃ or higher, and in a most preferred embodiment at least one Tg of 180 ℃ or higher.

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

In some embodiments, the mixture comprises at least one organic compound or polymer according to the invention and a singlet emitter, wherein the percentage by weight of the singlet emitter is 10% by weight or less, preferably 9% by weight or less, more preferably 8% by weight or less, particularly preferably 7% by weight or less, most preferably 5% by weight 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 is present in an amount of 25 wt.% or less, preferably 20 wt.% or less, more preferably 15 wt.% or less.

In another 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 luminescent materials in a weight ratio to the triplet emitter of from 1:2 to 2:1. In a further preferred embodiment, the energy level of the exciplex of the mixture according to the invention is higher than that of the phosphorescent emitter.

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

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 present invention may be used herein as the second host in an amount of 30 to 70% by weight.

The details of singlet emitters, triplet emitters, TADF materials and host materials in the present invention are described in WO2018095390A1.

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

wherein:

R ₁₃ selected from H, D, a straight chain alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a 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, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 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 or formula (8); and at least one R ₁₃ Has a structure shown in a structural formula (8);

Ar ⁴ ，Ar ⁵ 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 ⁴ ，Ar ⁵ ，L ₂ any two adjacent groups may be linked to each other to form a ring or not.

In one embodiment, ar ⁴ And L ₂ Are connected with each other to form a ring.

Further, H2 is selected from the following general formula:

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.

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

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, very preferably 1000g/mol or less, more preferably 950g/mol or less, and most preferably 900g/mol or less.

It is another object of the present invention to provide a material solution for printing 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, very preferably 1000g/mol or more, more preferably 1100g/mol or more, and 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, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that said 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 not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, 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, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, methyl benzoate, 4264-dimethylquinoline, 4234-methylquinoline, 4264-benzoic acid, ethyl benzoate, and the like.

Examples of aromatic ketone-based solvents suitable for the present invention are, but 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-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like.

Examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4- (1-propenyl) benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylnative ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4- (1-propenyl) -1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butylanisole, 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 at least one organic solvent may be selected from: aliphatic ketones, e.g., 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, 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 organic solvent may be selected 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. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned 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 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, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

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

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

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

δ _h (hydrogen bonding force) is 0.9-14.2 MPa ^1/2 In particular in the range of 2.0 to 6.0MPa ^1/2 In (c) is used.

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin 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 of the embodiments of the present invention may comprise from 0.01 to 10wt% of the organic compound or polymer or mixture according to the present invention, preferably from 0.1wt% to 15wt%, more preferably from 0.2wt% to 5wt%, most preferably from 0.25wt% to 3wt%.

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, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet 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, enhancing 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.

The present invention also provides a use of the Organic compound, polymer, mixture or composition as described above in an Organic electronic device, which may 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 spintronics, organic sensors, and Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present 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 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 as described above. The Organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (fet), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like, and particularly preferred are Organic electroluminescent devices such as OLED, OLEEC, and Organic light Emitting field effect transistor.

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

In certain preferred embodiments, the electroluminescent device comprises an organic compound as described above in the light-emitting layer, 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 described above, in particular an OLED, comprising 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. A substrate free of surface defects is 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 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. 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 pattern structured. 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 the n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a 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 cathodes in OLEDs 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, 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 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.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and 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 present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The synthesis of the compounds according to the invention is illustrated, but the invention is not limited to the following examples.

Synthesis example 1

1-3 Synthesis: mixing 1-1 (15.0 g), 1-2 (8.4 g), pd (PPh) ₃ ) ₄ (0.5 g) and potassium carbonate (14.0 g) were added to 200ml of a mixed solvent of 1, 4-dioxane/water (volume ratio 8:1) and refluxed for 12 hours under a nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining reaction solution was washed with water and extracted. Organic phase column chromatography to obtain 1-3.MS (ASAP): 339.79.

1-4 Synthesis: 1-3 (12.0 g) was dissolved in 100ml of triethyl phosphite and stirred at 140 ℃ for 12h. After cooling, most of the triethyl phosphite was distilled off under reduced pressure, washed with water and extracted with dichloromethane. Organic phase column chromatography to obtain 1-4.MS (ASAP): 307.80.

1-6 Synthesis: 1-4 (10.0 g), 1-5 (9.7 g), and cesium carbonate (14.0 g) were added to 140ml of dry DMF, and stirred at 140 ℃ for 6 hours. After cooling, water was added to precipitate. After filtration, the filter cake recrystallizes to yield 1-6.MS (ASAP): 588.13.

synthesis of Material 1: 1-6 (5.0 g) was dissolved in 120ml of 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 for 5h at 170 ℃ under a nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure. And pouring the residual reaction solution into a large amount of water, and filtering to obtain a filter cake. Recrystallization of the filter cake gives material 1.MS (ASAP): 551.67.

synthesis example 2

2-3 Synthesis of 1-3 in example 1, except that 1-1 was replaced with 2-1 and 1-2 was replaced with 2-2.

2-5 Synthesis: 2-3 (10.0 g), 2-4 (3.0 g), cuprous iodide (3.6 g), trans-cyclohexanediamine (4.4 g) and potassium phosphate (6.2 g) were added to dry toluene (150 ml), and the reaction was refluxed for 12 hours under a nitrogen atmosphere. Cooling, filtering, concentrating the filtrate by reduced pressure distillation, washing with water and extracting. After the organic phase is evaporated by rotation to remove the solvent, the intermediate 2-5 is obtained by recrystallization. MS (ASAP): 764.33.

synthesis of material 2 reference was made to the synthesis of material 1 in synthesis example 1, except that 1-6 was replaced with 2-5.MS (ASAP): 727.87.

synthesis example 3

3-2 Synthesis: mixing 1-4 (15.0 g), 3-1 (21.95 g), pd (OAc) ₂ (1.0 g), tri-tert-butylphosphine (2M, 2ml) and sodium tert-butoxide (12.0 g) were added to 300ml of dry toluene and the reaction was refluxed for 8 hours under a nitrogen atmosphere. After cooling, filtering, distilling and concentrating the reaction solution under reduced pressure, then washing and separating the solution, and carrying out organic phase column chromatography to obtain 3-2.MS (ASAP): 677.22.

synthesis of Material 3 reference is made to the synthesis of Material 1 of example 1, except that 1-6 is replaced by 3-2.MS (ASAP): 640.76.

synthesis example 4

Synthesis of 4-3 reference was made to the syntheses of 1-6 in example 1, except that 1-4 was replaced with 4-1 and 1-5 was replaced with 4-2.

Synthesis of material 4 reference is made to the synthesis of material 1 with the difference that 1-6 are replaced by 4-3.MS (ASAP): 691.79.

synthesis example 5

Synthesis of 5-2 reference was made to the synthesis of 2-5, except that 2-3 was replaced with 5-1.

The synthesis of material 5 refers to the synthesis of material 1, except that 1-6 is replaced with 5-2.MS (ASAP): 680.79.

synthesis example 6

Synthesis of 6-3 reference is made to the synthesis of 1-3, except that 1-1 is replaced by 6-2 and 1-2 is replaced by 6-1.

6, synthesis: 6-3 (5.0 g) was dissolved in 140ml of dry DMSO, DMAP (0.8 g) and cesium carbonate (5.3 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 washed with water and extracted. Organic phase column chromatography gave material 6.MS (ASAP): 574.69.

synthesis example 7

Synthesis of 7-3 reference was made to the synthesis of 2-5, except that 2-3 was replaced with 7-1 and 2-4 was replaced with 7-2;

synthesis of material 7 reference is made to the synthesis of material 1 with the difference that 1-6 is replaced by 7-3.MS (ASAP): 628.75.

synthesis example 8

8-3 Synthesis: 8-1 (5.0 g), 8-2 (3.6 g) and cesium carbonate (13.3 g) were dissolved in 150ml of DMF and stirred at 140 ℃ for 6h. After cooling, the reaction solution was concentrated by distillation under reduced pressure, and then the reaction solution was poured into a large amount of water, and the precipitated solid was filtered. The filter cake was extracted with dichloromethane and the layers were washed with water. Organic phase column chromatography to obtain 8-3.MS (ASAP): 452.31.

8-4 Synthesis: mixing 8-3 (6.0 g), pd (OAc) ₂ (0.4 g) and sodium tert-butoxide (2.0 g) tri-tert-butylphosphine (2M, 1ml) were added to 80ml of dry toluene and the reaction was refluxed for 8 hours under a nitrogen atmosphere. After cooling, filtering, distilling and concentrating the reaction solution under reduced pressure, then washing and separating the solution, and carrying out organic phase column chromatography to obtain 8-4.MS (ASAP): 371.40.

8-5 Synthesis: 8-4 (4.5 g) was dissolved in THF, and NBS (2.1 g) was dissolved in THF slowly dropwise with stirring at room temperature in the dark. Then stirred at room temperature for 2h. Washing the reaction solution with water, separating, and performing organic phase column chromatography to obtain 8-5.MS (ASAP): 450.30.

8-6 Synthesis: 8-5 (4.0 g), pinacol ester diboron (2.26 g), pd (dppf) Cl ₂ (0.1 g) and potassium acetate (1.7 g) were added to 1,4-dioxane (80 ml). And refluxing for 8h under a nitrogen atmosphere. After cooling, the reaction solution is concentrated by reduced pressure distillation and then subjected to column chromatography to obtain an intermediate 8-6.MS (ASAP): 497.36.

synthesis of Material 8 reference is made to the synthesis of 1-3, except that 1-2 is replaced with 8-6 and 1-1 is replaced with 8-7.MS (ASAP): 575.63. synthetic example 9:

synthesis of 9-3 reference was made to the synthesis of 3-2, except that 1-4 was replaced by 9-1 and 3-1 was replaced by 9-2.

Synthesis of material 9 reference is made to the synthesis of material 1 with the difference that 1-6 is replaced by 9-3.MS (ASAP): 651.08.

synthetic example 10:

synthesis of 10-3 reference was made to the synthesis of 3-2, except that 1-4 was replaced by 10-1 and 3-1 was replaced by 10-2.

The synthesis of material 10 is referenced to the synthesis of material 1, except that 1-6 is replaced with 10-3.MS (ASAP): 688.83.

synthetic example 11:

synthesis of 11-2: 11-1 (5.0 g) and 8-7 (2.1 g) were dissolved in 100ml of dry DMF, and NaH (0.6 g) was added in portions under a nitrogen atmosphere at 0 ℃ and stirred for 1 hour. Then the temperature is increased to 80 ℃ and the mixture is stirred for 6 hours. After cooling, the residual NaH was quenched by slow addition of water at 0 ℃, then the reaction was poured into a large volume of water and filtered. Recrystallizing the filter cake to obtain the material 11-2.MS (ASAP): 653.23.

synthesis of 11-3 reference was made to the synthesis of 2-5, except that 2-3 was replaced with 11-2.

The synthesis of material 11 is referenced to the synthesis of material 1, except that 1-6 is replaced with 11-3.MS (ASAP): 692.87.

2. organic Compound energy level calculation

The energy level of the organic compound material can be obtained by quantum calculation, for example, by Gaussian09W (Gaussian inc.) by using TD-DFT (including time density functional theory), and a specific simulation method can be found in WO2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (time-density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). HOMO and LUMO energy levels are calculated according to the following calibration equation, S ₁ ，T ₁ And a resonance factor f (S) ₁ ) Can be used directly.

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 the direct calculation of Gaussian09W, in Hartree. The results are shown in table 1:

table 1 molecular calculation of materials

As shown in Table 1, the LUMO energy levels of the materials 1 to 11 are all in the range of-2.86 to-3.02 eV, the HOMO energy level is in the range of-5.25 to-5.75 eV, and the triplet energy levels are all higher than 2.20eV, which indicates that the materials can be used as bipolar red host materials. In addition, the HOMO levels of the materials 1 to 6, 9 to 11 were in the range of-5.25 to-5.50V, which is more favorable for the transport of holes from the hole transport layer to the light emitting layer than the material of comparative example 1 (HOMO level-5.71 eV). The LUMO levels of materials 1 to 11 were better matched to the electron transport layer relative to the LUMO level (-2.51 eV) of comparative example 1. H2-1 and H2-2 are two materials which satisfy the general formula of H2 in the invention. The material 3, the material 4, the material 5 and the material 8 are respectively blended with H2-1, or the material 8 is blended with H2-2, and all the conditions of min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)) +0.1eV are met, so that the mixture of the materials and H2-1 or H2-2 can form exciplex as a co-host material.

3. Device preparation and detection

Device example 1

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

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. HATCN (30 nm), HTM (50 nm), host material RD (40 nm), ETM Liq (30 nm), liq (1 nm), al (100 n)m) in high vacuum (1X 10) ^-6 Millibar) hot evaporation;

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

Preparation of an OLED device reference was made to device example 1 except that the host material was changed to the compound shown in table 2 or the blended mixture in a mass ratio of 1:1.

Table 2: OLED device Performance comparison

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. Table 2 shows the OLED device lifetime and external quantum efficiency comparison, where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. Here, LT95, external quantum efficiency were calculated in comparison with device example 12 (corresponding to comparative example 1), that is, with the lifetime of device example 12 being 1 and the external quantum efficiency being 100. Device examples 1-11 have significantly higher out-of-device quantum efficiencies and lifetimes than device example 12 (corresponding to comparative example 1). The material shown in the invention has a seven-membered ring conjugated system with an electron donating property and an electron-withdrawing substituent, so that the material has balanced hole and electron transport capabilities, and the comparative example material lacks the electron-withdrawing substituent, so that the hole and electron transport is unbalanced. Among them, the device lifetime of device examples 2 to 11 is significantly higher than that of other single-host examples (corresponding to example 1, example 12 to example 14) because the compounds used in these examples have a larger fused ring system and better stability, and the transport ability of carriers between molecules is better. Device example 15 (mixture of corresponding material 4-1 in mass ratio 1:1), device example 16 (mixture of corresponding material 8-2 in mass ratio 1:1) using the mixture of the present invention as a co-host had the highest device lifetime and external quantum efficiency (both exceeding 25%), because the co-host had relatively more balanced hole/electron transport properties and an exciplex having TADF effect was formed in the energized state, increasing exciton utilization efficiency. Therefore, the OLED device prepared by the organic mixture provided by the invention has obviously improved luminous efficiency and service life.

Claims (9)

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

（1）

wherein:

Ar ¹ - Ar ³ each independently selected from the general formula (A-1) or (A-3):

；

x is independently selected from CR for each occurrence ¹ (ii) a And X is C when X is a linking site;

y is selected from O or S;

Y ₁ 、Y ₂ one of which is a single bond and the other is NR ⁴ ；

At Ar of ¹ One of R in ¹ Or R ⁴ Selected from the general formula (B-2), the remaining R ¹ And the rest of R ⁴ Is selected from H;

X ₁ each occurrence is independently selected from CR ⁶ Or N; and X ₁ Is a connecting siteWhen, X ₁ Is C; x in the general formula (B-2) ₁ The parent ring of (a) is quinoxalinyl or benzopyrimidinyl;

L ₁ selected from single bonds;

R ⁶ selected from the group consisting of H, D, a straight chain alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, a hydroxyl group, a nitro group, a CF group ₃ A group, cl, br, F, an aromatic group having 5-40 ring atoms, an aryloxy group having 5 to 40 ring atoms, or a combination of these systems;

* Indicates the attachment site.

2. An organic compound according to claim 1, wherein Y is selected from S.

3. The organic compound according to claim 1, wherein the general formula (B-2) is selected from the following structures:

；

X ₁ is selected from CH.

4. The organic compound of claim 3, wherein R is ⁶ Selected from benzene.

5. The organic compound of claim 1, wherein the organic compound is selected from the following structures:

。

6. a mixture comprising an organic functional material H1, said organic functional material H1 being selected from the organic compounds according to any one of claims 1 to 5, and another organic functional material H2, said another organic functional material H2 being selected from the host material.

7. The mixture of claim 6, wherein the other organic functional material H2 comprises a structure according to formula (7):

wherein:

R ₁₃ selected from the group consisting of H, D, a straight chain alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a branched or cyclic alkyl 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, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, a hydroxyl group, a nitro group, CF ₃ A group, cl, br, F, an 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 or formula (8); and at least one R ₁₃ Has a structure shown in a structural formula (8);

Ar ⁴ ，Ar ⁵ each independently selected from an aromatic group having 6 to 30 ring atoms, a heteroaromatic group having 5 to 30 ring atoms, or a non-aromatic ring group having 5 to 30 ring atoms;

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

Ar ⁴ ，Ar ⁵ ，L ₂ wherein any two adjacent groups are linked to each otherWith or without looping.

8. A composition comprising at least one of the organic compounds according to any one of claims 1 to 5 and the mixtures according to any one of claims 6 to 7, and at least one organic solvent.

9. An organic electronic device comprising at least one of the organic compounds according to any of claims 1 to 5, the mixtures according to any of claims 6 to 7, or prepared from the composition according to claim 8.