CN112724152B

CN112724152B - Nitrogen-containing heterocyclic organic compound and application thereof

Info

Publication number: CN112724152B
Application number: CN202011077295.4A
Authority: CN
Inventors: 张晨; 萧锡辉; 李灿楷
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2019-10-28
Filing date: 2020-10-10
Publication date: 2022-06-07
Anticipated expiration: 2040-10-10
Also published as: CN112724152A

Abstract

The present invention relates to the field of electroluminescence, and in particular to organic compounds containing nitrogen heterocycles, polymers, mixtures and compositions comprising the same, and their use in organic electronic devices. The organic compound can be used as a main body material to be applied to electroluminescent devices, particularly OLED devices. The organic compounds according to the invention can be used to increase the luminous efficiency and the lifetime of electroluminescent devices by complexing them with suitable guests, in particular phosphorescent guests or TADF emitters. The invention provides a solution for a light emitting device with low manufacturing cost, high efficiency, long service life and low roll-off.

Description

Nitrogen-containing heterocyclic organic compound and application thereof

The present application claims priority from a chinese patent application filed in 2019, 28/10, having application number 201911029851.8 entitled "a nitrogen-containing heterocyclic organic compound and its use in organic electronic devices", the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to a nitrogen heterocyclic ring organic compound and application thereof.

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 a wide viewing angle, a fast response time, a low operating voltage, a thin panel thickness, and the like in the field of 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 light emitting material systems based on fluorescence and phosphorescence have been developed, and the organic light emitting diode using a fluorescent material has a high reliability but is limited in its internal electroluminescence quantum efficiency to 25% under electrical excitation because the ratio of the singlet excited state to the triplet excited state of the current-generated exciton 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 as a host material for phosphorescent substances. 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 designs, people tend to adopt a material containing an electron transport group and a hole transport group which are combined to be designed into a bipolar transport main body, which is beneficial to the balance of charge transport, such as the triazine or pyrimidine derivatives disclosed in patents US2016329506, US20170170409 and the like, or the 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 above-mentioned shortcomings of the prior art, the present invention aims to provide a class of organic compounds, polymers, mixtures, compositions and applications thereof based on nitrogen-containing heterocycles, and aims to provide a new class of host materials, which can improve the stability and lifetime of devices.

The technical scheme of the invention is as follows:

an N-containing organic compound having a structure represented by general formula (1):

wherein:

Ar¹、Ar²、Ar³each independently selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms or a substituted or unsubstituted heteroaromatic group having 6 to 20 ring atoms;

z is selected from CR₂Or N;

R₁-R₂each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF₃、Cl、Br、F、A crosslinkable group, or a substituted or unsubstituted aromatic group having from 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, or an aryloxy group having from 5 to 40 ring atoms, or a heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; adjacent R₁May be interconnected to form a ring.

The present invention further relates to a polymer comprising at least one repeating unit containing a structural unit represented by the general formula (1).

The invention further relates to a mixture comprising an organic functional material H1 and at least one further organic functional material H2; the H1 is selected from the organic compound or the high polymer as described in any one of the above; the other organic functional material H2 is selected from Hole Injection Material (HIM), Hole Transport Material (HTM), Electron Transport Material (ETM), Electron Injection Material (EIM), Electron Blocking Material (EBM), Hole Blocking Material (HBM), luminophor (Emitter) or Host material (Host).

A composition comprising an organic compound or polymer or mixture as defined in any one of the preceding claims and at least one organic solvent.

An organic electronic device comprising an organic compound or polymer or mixture as defined in any preceding claim.

Has the advantages that:

the organic compound according to the present invention can be used as a host material, and can improve the luminous efficiency and the lifetime of an electroluminescent device by being matched with a suitable guest, particularly a phosphorescent guest or a TADF luminophore. The invention provides a solution for a light emitting device with low manufacturing cost, high efficiency, long service life and low roll-off. In addition, the organic matter of the invention is used as a main body material, and is matched with another main body with hole transmission property or bipolar property to form a common main 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 accompanying examples. 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 containing a nitrogen heterocyclic structure 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 schemes 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 are not intended to 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, singlet states and singlet states have the same meaning and may be interchanged.

In the present embodiment, the triplet state and the triplet state have the same meaning and are interchangeable.

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_1-30Alkyl, heterocyclic group containing 3 to 20 ring atoms, aryl group containing 5 to 20 ring atoms, heteroaryl group containing 5 to 20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, -NRR', cyano group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate groupAn ester group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted with 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_1-6An 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_1-6Alkyl, 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_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 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 condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. 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 radicals 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 aromatic ring 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 present invention, "+" attached to a single bond represents a connection 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 a fused site is not specified in a group, it means that an optionally fused site in the group is a fused site, and preferably two or more sites in the ortho-position in the group are fused sites;

in the invention, the single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position of the ring, e.g.

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

In

And

wherein any C atom on the phenyl ring is fused.

In the embodiment of the present invention, the energy level structure of the organic material, 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.

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 triplet energy level ET1 of the organic material may be measured by low temperature Time resolved luminescence spectroscopy, or may be obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian09W (Gaussian Inc.), specific simulation methods may be found in WO2011141110 or as described in the examples below.

It should be noted that the absolute values of HOMO, LUMO, ET1 depend on the measurement or calculation method used, and even for the same method, different methods of evaluation, e.g. starting point and peak point on the CV curve, may 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, the values of HOMO, LUMO, ET1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

The invention relates to an N-containing organic compound, which has a structure shown as a general formula (1):

wherein:

z is selected from CR₂Or N;

R₁-R₂each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₁May be interconnected to form a ring.

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

in one embodiment, Z is selected from CR₂(ii) a Further, R₂Selected from H, methyl or phenyl.

In another preferred embodiment, Z is selected from N.

in a certain preferred embodiment, Ar¹、Ar²、Ar³Each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 15 ring atoms; in a certain preferred embodiment, Ar¹、Ar²、Ar³At least one of them is selected from substituted or unsubstituted phenyl; in a certain preferred embodiment, Ar¹、Ar²、Ar³At least two of which are selected from substituted or unsubstituted phenyl; in a certain preferred embodiment, Ar¹、Ar²、Ar³Are all selected from substituted or unsubstituted phenyl.

In a certain preferred embodiment, Ar¹、Ar²、Ar³At least one of which is selected from a substituted or unsubstituted fused ring aromatic group having 10 to 20 ring atoms, or a substituted or unsubstituted fused ring heteroaromatic group having 10 to 20 ring atoms; in a certain preferred embodiment, Ar¹、Ar²、Ar³Wherein at least two are selected from substituted or unsubstituted fused ring aromatic groups having 10 to 20 ring atoms, or substituted or unsubstituted fused ring heteroaromatic groups having 10 to 20 ring atoms; in a certain preferred embodiment, Ar¹、Ar²、Ar³One of which is selected from a substituted or unsubstituted fused ring aromatic group having 10 to 20 ring atoms, or a substituted or unsubstituted fused ring heteroaromatic group having 10 to 20 ring atoms, and the other two are selected from a substituted or unsubstituted phenyl group; in a certain preferred embodiment, Ar¹、Ar²、Ar³Two of them are selected from substituted or unsubstituted fused ring aromatic groups having 10 to 20 ring atoms, or substitutedOr an unsubstituted fused ring heteroaromatic group having 10 to 20 ring atoms, the other selected from substituted or unsubstituted phenyl.

In the present invention, substituted means substituted by R, R has the same meaning as R₁。

In a certain preferred embodiment, Ar¹、Ar²、Ar³Each independently selected from any one of (A-1) to (A-6):

wherein:

X₁at each occurrence, is independently selected from N or CR₃(ii) a Preferably, X₁At each occurrence, is independently selected from CR₃；

Y₁、Y₂Independently selected from single bond, NR₄、CR₄R₅、SiR₄R₅、O、S、S(＝O)₂Or S (═ O);

R₃-R₅each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₃Can be combined withAre interconnected to form a ring.

Further, Ar¹、Ar²、Ar³Each independently selected from the group consisting of:

in a certain preferred embodiment, Ar¹、Ar²、Ar³Each independently selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-1), Ar²Selected from (A-1), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-1), Ar²Selected from (A-2), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-1), Ar²Selected from (A-3), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-2), Ar²Selected from (A-1), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-2), Ar²Selected from (A-2), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-2), Ar²Selected from (A-3), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-3), Ar²Selected from (A-1), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-3), Ar²Selected from (A-2), Ar³Selected from (A-1), (A-2) or (A-3);

preferably, Ar¹Selected from (A-3), Ar²Selected from (A-3), Ar³Is selected from (A-1), (A-2) or (A-3).

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

wherein:

ar in the general formula (2-2)¹And Ar²At least one selected from any one of (A-2) to (A-6);

ar in the general formula (2-3)¹And Ar³At least one selected from any one of (A-2) to (A-6);

ar in the general formula (2-4)²And Ar³At least one selected from any one of (A-2) to (A-6).

Further, the general formula (1) is selected from any one of (3-1) to (3-11):

in one embodiment, the general formula (1) is selected from any one of the following structures;

in a certain preferred embodiment, X in the general formula (2-1) or (3-1) - (3-9)₁Are all selected from CR₃(ii) a Preferably, at least one R₃Selected from a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms; more preferably, at least one R₃Selected from substituted or unsubstituted N-containing heteroaromatic groups having from 5 to 40 ring atoms.

In a certain preferred embodiment, at least one, and at most 4, X of formula (2-1) or (3-1) - (3-9)₁Are all selected from N; preferably, at least one R₃Selected from a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms; more preferably, at least one R₃Selected from substituted or unsubstituted N-containing heteroaromatic groups having from 5 to 40 ring atoms.

preferably, R₃Selected from the following groups:

wherein:

L₁represents a single bond, 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;

X₂at each occurrence, is independently selected from N or CR₆；

Y₃Selected from single bonds, NR₇、CR₇R₈、SiR₇R₈、O、S、S(＝O)₂Or S (═ O);

R₆-R₈each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₆May be interconnected to form a ring.

Further, R₃Selected from the following groups:

in one embodiment, L₁Selected from single bonds or phenyl or pyridyl.

In one embodiment, R₆Selected from phenyl.

In a preferred embodiment, there is a pair of adjacent R₁Are connected with each other to form a ring; preferably, formula (1) is selected from the following formulae:

preferably, R₁Selected from substituted or unsubstituted aromatic groups having 5 to 40 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 40 ring atoms.

The N-containing organic compounds according to the present invention are preferably selected from, but not limited to, the following structures, which may be optionally substituted:

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

The N-containing organic compounds according to the invention can be used as functional materials 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 N-containing 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, the N-containing compounds according to the invention, E thereof_T1Not less than 2.2 eV; more preferably at least 2.4eV, still more preferably at least 2.6 eV.

In a preferred embodiment, an N-containing organic compound according to the present invention needs to have a suitable resonance factor f (S1) to facilitate the transfer of excitons from host to guest, thereby improving 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 another preferred embodiment, an N-containing organic compound according to the invention requires a relatively modest singlet-triplet energy level difference Δ E_STThereby facilitating the transfer of excitons from the host to the guest and improving the luminous efficiency of the device. Preferably,. DELTA.E_STLess than or equal to 0.9eV, preferably Delta E_ST0.6eV or less, preferably,. DELTA.E_ST≤0.4eV。

When the N-containing organic compound according to the present invention is used as a host material, appropriate Δ HOMO and Δ LUMO are required.

In certain preferred embodiments, the compounds according to the invention,. DELTA.HOMO, (. DELTA.HOMO- (HOMO-1)), is preferably ≧ 0.1eV, more preferably ≧ 0.25eV, and most preferably ≧ 0.40 eV.

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

In some embodiments, the N-containing organic compounds according to the present invention have a light emitting function with a light emitting wavelength of 300 to 1000nm, preferably 350 to 900nm, and more preferably 400 to 800 nm. Luminescence as used herein refers to 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 more, preferably 120 ℃ or more, more preferably 140 ℃ or more, more preferably 160 ℃ or more, most preferably 180 ℃ or more.

In a preferred embodiment, the polymer according to the invention preferably has a molecular weight distribution (PDI) in the range of 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, which comprises an organic functional material H1, H1 is selected from the N-containing organic compounds or high polymers, and at least another organic functional material H2. The organic functional material H2 is selected from Hole Injection Material (HIM), Hole Transport Material (HTM), Electron Transport Material (ETM), Electron Injection Material (EIM), Electron Blocking Material (EBM), Hole Blocking Material (HBM), luminophor (Emitter) and 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 which 3 are hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain preferred embodiments, the mixtures according to the invention in which at least one of H1 and H2 has a Δ LUMO > 0.1eV, preferably > 0.2eV, more preferably > 0.2 eV.

In a preferred embodiment, the mixtures according to the invention, where H1 has a Δ LUMO of 0.1eV or more, preferably 0.2eV or more, more preferably 0.3eV or more.

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

In a preferred embodiment, the mixtures according to the invention, in which H2 has a. DELTA. HOMO > 0.1eV, preferably > 0.25eV, more preferably > 0.4 eV.

In certain preferred embodiments, the 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, the highest occupied orbital, the energy level of the triplet state of H1, LUMO (H2), HOMO (H2) and ET (H2) are the lowest unoccupied orbital, the highest occupied orbital, the energy level of the triplet state of H2, respectively, more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)), still more preferably ((LUMO (H1) -HOMO (2), LUMO (H1)) ≦ ET (H2)) +0._T(H1),E_T(H2))-0.1eV；

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

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

In a preferred embodiment, the mixture wherein the molecular weights of H1 and H2 differ by no more than 100Dalton, preferably no more than 80Dalton, more preferably no more than 70Dalton, more preferably no more than 60Dalton, most preferably no more than 40Dalton, most preferably no more than 30 Dalton.

In another preferred embodiment, the mixture wherein the difference between the sublimation temperatures of H1 and H2 is no more than 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 temperatures does not exceed 10K.

In a preferred embodiment, at least one of H1 and H2 in the mixture according to the invention has a Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 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 one triplet emitter in a proportion by weight of 25% or less, preferably 20% or less, more preferably 15% 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 embodiments, 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 as the second host, and may be 30 to 70% by weight.

The details of singlet emitters, triplet emitters, TADF materials and host materials are described in WO2018095390a 1.

In certain preferred embodiments, the mixture, the another organic functional material H2 comprises a structure according to formula (4):

wherein when R is¹-R⁹Each occurrence is independently selected from (4-1), a hydrogen atom, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkyloxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, a substituted aryl group, an heteroaryl group, a substituted aryl group, a substituted aryl group, a substituted aryl group and the aryl group and,Isocyanates, thiocyanates, isothiocyanates, hydroxyls, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R¹-R⁹Can be connected with each other to form a ring; and R is¹-R⁹At least one of them is selected from the structural formula (4-1);

Ar⁴and Ar⁵Each independently selected from a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring group having 5 to 30 ring atoms;

L₂selected from a single bond, a substituted or unsubstituted aryl group having 5 to 30 ring atoms, or 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;

Ar⁴、Ar⁵、L₂any two of which may be interconnected to form a ring.

Further, H2 is selected from the following formulas:

further, H2 is selected from the following formulas:

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 N-containing 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 N-containing organic compounds according to the 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 N-containing 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 N-containing 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-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, 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 dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the 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, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; 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) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

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

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

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 10 wt%, preferably from 0.1 to 15 wt%, more preferably from 0.2 to 5 wt%, most preferably from 0.25 to 3 wt%, of the N-containing organic compound or polymer or mixture according to the present invention.

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., reference is made to the Handbook of Print Media, technology and Production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

The present invention also provides the use of an N-containing 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 (efets), Organic lasers, Organic spintronics, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., particularly preferably 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 N-containing organic compound, polymer or mixture as described above, or prepared from a 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 N-containing organic compound 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 (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

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

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

In the above-mentioned light emitting device, especially an OLED, it 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, p 2606. 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 0.2 eV. 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 the Electron Injection Layer (EIL) or the Electron Transport Layer (ETL) or the Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.5eVLess than 0.3eV, preferably less than 0.2 eV. 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, BaF₂Al, 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.

Example 1

Synthesis of intermediates 1 to 3: 1-1(20.0g) and 1-2(43.8g) were dissolved in dry DMF, and cesium carbonate (38.46g) was added to conduct a reaction at 140 ℃ for 8 hours. After cooling, the solvent is removed by reduced pressure distillation, the residual reaction solution is washed by water and extracted, and the intermediate 1-3 is obtained by recrystallization after the solvent is removed by organic phase rotary evaporation.

Synthesis of Compound 1: intermediates 1 to 3(10.0g), Pd (PCy)₃)₂Cl₂(CAS 78655-99-9, 1.2g), isovaleric acid (1.1g), cesium carbonate (10.0g) were added to 100ml of dry DMAC and stirred at 170 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by distillation under reduced pressure, the liquid is extracted and washed by water, and the organic phase is subjected to rotary evaporation to remove the solvent and then recrystallized to obtain the compound 1. Ms (asap): 602.

example 2

Synthesis of intermediates 2 to 3: intermediate 2-1(20.0g), 2-2(16.6g), DMAP (3.17g) were dissolved in dry DMSO, and cesium carbonate (33.0g) was added and heated to 100 ℃ under a nitrogen atmosphere for reaction for 8 h. After cooling, most of the solvent was distilled off under reduced pressure. Washing and extracting residual reactants, removing the solvent by rotary evaporation of an organic phase, and recrystallizing to obtain an intermediate 2-3.

Synthesis of material 2 reference is made to the synthesis of material 1 of example 1, except that 1-3 is replaced by 2-3. Ms (asap): 588.

example 3

Synthesis of intermediate 3-2: mixing 3-1(15.0g), pinacol diborate (9.3g), Pd (dppf) Cl₂([1,1' -bis (diphenylphosphino) ferrocene)]Palladium dichloride (1.2 g) and potassium acetate (4.9g) were added to 1, 4-dioxane and reacted at 100 ℃ for 8 hours under a nitrogen atmosphere. Cooling, distilling under reduced pressure to remove most of the solvent, washing the residual reaction solution with water, extracting, and removing the organic phase by rotary evaporationRecrystallizing after solvent to obtain the intermediate 3-2.

Synthesis of intermediates 3 to 4: mixing 3-2(10.0g), 3-3(5.2g), Pd (PPh)₃)₄(tetrakis (triphenylphosphine) palladium, 0.8g) and potassium carbonate (4.2g) were added to 1, 4-dioxane, and the appropriate amount of water was added. The reaction was carried out for 8h at 100 ℃ under a nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, the remaining reaction solution was extracted by washing with water, and the solvent was removed by rotary evaporation of the organic phase, followed by recrystallization to obtain an intermediate 3-4.

Synthesis of Material 3: intermediate 3-4(8.0g) was dissolved in dry DMF and cesium carbonate (6.6g) was added. Reacting at 140 ℃ for 6h, cooling, distilling under reduced pressure to remove most of the solvent, washing and extracting the residual reaction solution with water, and then carrying out organic phase rotary evaporation to remove the solvent and recrystallizing to obtain the material 3. Ms (asap): 575.

example 4

Synthesis of intermediate 4-3 referring to the synthesis of 1-3 in example 1, except that 1-1 was changed to 4-1 and 1-2 was changed to 4-2; synthesis of Material 4 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was changed to 4-3. Ms (asap) of material 4: 618.

example 5

Synthesis of intermediate 5-3 reference was made to the synthesis of 1-3 in example 1, except that 1-1 was changed to 5-1 and 1-2 was changed to 5-2; synthesis of Material 5 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was changed to 5-3. Ms (asap) of material 5: 652.

example 6

Synthesis of intermediate 6-2 reference was made to the synthesis of 2-3 in example 2, except that 2-1 was changed to 6-1; synthesis of Material 6 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was replaced by 6-2. Mass spectrum ms (asap) of material 6: 667.

example 7

Synthesis of intermediate 7-3 reference was made to the synthesis of 1-3 in example 1, except that 1-1 was changed to 7-1 and 1-2 was changed to 7-2; synthesis of Material 5 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was changed to 7-3. Ms (asap) of material 7: 689.

example 8

Synthesis of intermediate 8-2 reference was made to the synthesis of 1-3 in example 1, except that 1-1 was changed to 4-1 and 1-2 was changed to 8-1; synthesis of Material 5 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was changed to 8-2. Ms (asap) of material 8: 562.

example 9

Synthesis of intermediate 9-2 reference was made to the synthesis of 1-3 in example 1, except that 1-1 was changed to 9-1 and 1-2 was changed to 9-2; synthesis of Material 9 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was changed to 9-3. Ms (asap) of material 9: 665.

example 10

Synthesis of intermediate 10-1 reference was made to the synthesis of 2-3 in example 2, except that 2-1 was changed to 1-1; synthesis of Material 10 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was replaced with 10-1. Ms (asap) of material 10: 422.

example 11

Synthesis of intermediate 11-3 reference was made to the synthesis of 1-3 in example 1, except that 1-1 was changed to 11-1 and 1-2 was changed to 11-2; synthesis of Material 11 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was replaced with 11-3. Ms (asap) of material 11: 612.

example 12

Synthesis of intermediate 12-2: 12-1(15.0g), pinacol ester diboron (13.4g), Pd (dppf) Cl₂(1.1g) and potassium acetate (7.7g) were added to 400ml of 1, 4-dioxane, and the mixture was stirred at 100 ℃ for 8 hours under a nitrogen atmosphere. After cooling, most of the solvent is removed by reduced pressure distillation, and after washing and extraction of the residual reaction liquid, the intermediate 12-2 is obtained by recrystallization of the organic phase. Synthesis of intermediate 12-4: mixing 12-2(12.0g), 12-3(20.7g), Pd (PPh)₃)₄(1.1g) and potassium carbonate (10.0g) were added to a mixed solvent of 1, 4-dioxane and water, and the mixture was stirred at 100 ℃ for 12 hours under a nitrogen atmosphere. After cooling, most of the solvent is removed by reduced pressure distillation, and after washing and extraction of residual reaction liquid, the intermediate 12-4 is obtained by recrystallization of the organic phase. Synthesis of Material 12: 12-4(10.0g) and cesium carbonate (6.07g) were added to DMF, and the mixture was heated to 130 ℃ and stirred for 6 hours. After cooling, most of the solvent is removed by reduced pressure distillation, and after washing and extraction of residual reaction liquid, the intermediate 12-4 is obtained by recrystallization of the organic phase. Ms (asap): 678.

example 13

Synthesis of intermediate 13-2 reference was made to the synthesis of 1-3 in example 1-except that 1-1 was changed to 4-1 and 1-2 was changed to 13-1; synthesis of Material 13 reference was made to the synthesis of Material 1 in example 1, except that 1-3 was replaced with 13-2. Ms (asap) of material 13: 523.

example 14

Synthesis of intermediate 14-2 reference was made to example 12, the synthesis of intermediate 12-4, except that 12-3 was changed to 14-1; synthesis of Material 14 reference is made to the synthesis of material 12 in example 12, except that 12-4 is replaced by 14-2. Ms (asap) of material 14: -523.

Example 15

Synthesis of intermediate 15-2 reference was made to the synthesis of intermediate-1-3 of example 1, except that 1-1 was replaced with 4-1 and 1-2 was replaced with 15-1; synthesis of Material 15 reference is made to the synthesis of Material 1 in example 1, except that 1-3 is replaced by 15-2. Ms (asap) of material 15: 730.

1. organic Compound energy level calculation

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. 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 (including 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). The HOMO and LUMO energy levels are calculated according to the following calibration equation, S₁，T₁And 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

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results are shown in table 1:

table 1 molecular calculation of materials

As shown in Table 1, the LUMO levels of the materials 1 to 10 and 12 are all in the range of-2.75 to-3.05 eV, and the triplet levels are all higher than 2.20eV, indicating that these materials can be used as n-type red host materials. In addition, the HOMO energy levels of the materials 1-3, 6, 9 and 11-15 are in the range of-5.20 to-5.65 eV, and the material can be used as a p-type red light host material. The difference of the triplet state and singlet state energy levels of the materials 1 to 3, 9, 10 and 12 is less than 0.3eV, and the TADF sensitized solar cell can be used as a TADF sensitized main body. Materials 3, 9, 10 and 12 were blended with H2-1 and materials 10 and 12 were blended with H2-2, respectively, all of which satisfy the condition of min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)) +0.1 eV), indicating that mixtures of these materials with H2-1 or H2-2 can form exciplex compounds as co-host materials.

2. Device preparation and detection

Device example 1

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

a. cleaning the conductive glass substrate, wherein when the conductive glass substrate is used for the first time, the conductive glass substrate can be cleaned by various solvents, such as chloroform, ketone and isopropanol, and then is subjected to ultraviolet ozone plasma treatment;

b. HATCN (30nm), HTM (50nm), host material RD (40nm), ETM Liq (30nm), Liq (1nm), Al (100nm) in high vacuum (1X 10)^-6Millibar) 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 mixture blended 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, the external quantum efficiency, was calculated by comparing the lifetime of device example 16 (corresponding to the material shown in comparative example 1) to 100, that is, the external quantum efficiency was calculated by taking the lifetime of device example 16 as 1. Device example 1-example 15 and device example 17-example 20 had significantly higher out-of-device quantum efficiencies and lifetimes than device example 16 (corresponding to comparative example 1). This is because the compound of the present invention has a larger conjugated structure than the compound used in the comparative example, and thus has a better carrier transport efficiency. Among them, the device life time of device example 3, device example 9, device example 10, and device example 12 is significantly higher than that of the other examples because the compounds used in these examples have suitable Δ Ε_ST(<0.2 eV). Co-host devices using the materials of the present invention (corresponding to examples 17-17)20) Has the highest device lifetime and external quantum efficiency (both over 25%) because the co-host has relatively more balanced hole/electron transport properties and forms exciplex 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.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. An N-containing organic compound characterized by: has a structure represented by the general formula (1):

wherein:

z is selected from CR₂Or N;

R₁-R₂each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atomsA linear thioalkoxy group, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF₃Cl, Br, F, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₁May be interconnected to form a ring.

2. The N-containing organic compound of claim 1, wherein: the general formula (1) is selected from any one of the following structures:

3. the N-containing organic compound of claim 1, wherein: ar (Ar)¹、Ar²、Ar³At least one of which is selected from a substituted or unsubstituted fused ring aromatic group having 10 to 20 ring atoms, or a substituted or unsubstituted fused ring heteroaromatic group having 10 to 20 ring atoms.

4. The N-containing organic compound of claim 1, wherein: ar (Ar)¹、Ar²、Ar³Each independently selected from any one of (A-1) to (A-6):

wherein:

X₁at each occurrence, is independently selected from N or CR₃；

R₃-R₅each occurrence is independently selected from H, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF₃Cl, Br, F, or a substituted or unsubstituted aromatic group having from 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, or an aryloxy group having from 5 to 40 ring atoms, or a heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; adjacent R₃May be interconnected to form a ring.

5. The N-containing organic compound of claim 4, wherein: the general formula (1) is selected from any one of general formulas (2-1) to (2-4):

wherein: ar in the general formula (2-2)¹And Ar²At least one selected from any one of (A-2) to (A-6); ar in the general formula (2-3)¹And Ar³At least one selected from any one of (A-2) to (A-6); general formula (2-4)) Middle Ar²And Ar³At least one selected from any one of (A-2) to (A-6).

6. The N-containing organic compound of claim 5, wherein: the general formula (1) is selected from any one of (3-1) to (3-11):

7. the N-containing organic compound of claim 5, wherein: the general formula (1) is selected from any one of the following structures:

8. the N-containing organic compound of claim 6 or 7, wherein: x₁Are all selected from CR₃And R is₃Selected from H or the following groups:

wherein:

X₂at each occurrence, is independently selected from N or CR₆；

R₆-R₈each occurrence is independently selected from H, or D, or a linear alkyl having 1 to 20C atomsOxy, or linear thioalkoxy having 1 to 20C atoms, or branched or cyclic alkyl having 3 to 20C atoms, or branched or cyclic alkoxy having 3 to 20C atoms, or branched or cyclic thioalkoxy having 3 to 20C atoms, or silyl, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, or cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF, or a salt thereof₃Cl, Br, F, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₆May be interconnected to form a ring.

9. The N-containing organic compound of claim 8, wherein: at least one R₃Selected from the following groups:

10. a mixture, characterized by: comprises an organic functional material H1 and at least another organic functional material H2; said H1 is selected from the N-containing organic compounds of any one of claims 1 to 9; the other organic functional material H2 is selected from hole injection material, hole transport material, electron injection material, electron blocking material, hole blocking material, light emitter or host material.

11. The mixture according to claim 10, wherein: the other organic functional material H2 comprises a structure shown as a general formula (4):

wherein when R is¹-R⁹Each occurrence is independently selected from (4-1), a hydrogen atom, or D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or 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, or a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxy group, a hydroxyl group, a carboxyl group, a CF, a hydroxyl group, a carboxyl group, a hydroxy group, a mercapto group, a hydroxy₃Cl, Br, F, or a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems;

adjacent R¹-R⁹Can be connected with each other to form a ring; and R is¹-R⁹At least one of them is selected from the structural formula (4-1);

Ar⁴、Ar⁵、L₂any two of which may be interconnected to form a ring.

12. A composition characterized by: comprising an N-containing organic compound according to any one of claims 1 to 9 or a mixture according to any one of claims 10 to 11, and at least one organic solvent.

13. An organic electronic device, characterized by: comprising an N-containing organic compound according to any one of claims 1 to 9 or a mixture according to any one of claims 10 to 11 or prepared from a composition according to claim 12.