CN114085228A

CN114085228A - Organic compound containing nitrogen heterocycle, mixture, composition and application

Info

Publication number: CN114085228A
Application number: CN202010867376.8A
Authority: CN
Inventors: 张晨; 李灿楷; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2020-08-25
Filing date: 2020-08-25
Publication date: 2022-02-25

Abstract

The invention relates to an organic compound containing nitrogen heterocycle, a mixture, a composition and application thereof. The compound has a structural general formula shown in a chemical formula (1), has good stability, high luminous efficiency, long service life and simple synthesis, and can effectively improve the performance of an organic electronic device when being used in the organic electronic device.

Description

Organic compound containing nitrogen heterocycle, mixture, composition and application

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic compound containing a nitrogen heterocycle, a mixture, a composition 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 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 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 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 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 prior art material designs, one tends to use a composition containing an electron transport group and a hole transport group, designed as a host of bipolar transport, beneficial to the balance of charge transport, as described in patents US2016329506, US20170170409, etc., or as a class of triazine or pyrimidine derivatives disclosed in patent CN 104541576A. Although bipolar transport molecules are used as a host, good device performance can be obtained, but the obtained device performance and lifetime are still to be improved, and therefore, development of new host materials is urgently needed.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide organic compounds, polymers, mixtures, compositions and uses containing nitrogen heterocycles, which are intended to solve the problems of efficiency and lifetime of the existing OLEDs.

The technical scheme is as follows:

an organic compound containing nitrogen heterocycle, which has a structural general formula shown in formula (1):

wherein,

x is independently selected from CR at each occurrence₁Or N;

Y₁selected from the group consisting of CR₂R₃、NR₄O or S;

Y₂selected from single bond, CR₂R₃O or S;

R₁to R₄Each occurrence is independently selected from a hydrogen atom, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, a CF group, a hydroxyl group, a nitro group, a hydroxyl group, a sulfo group or an isothiocyanate group₃，Cl，Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₁With or without a ring of interconnects.

A polymer comprising at least one repeating unit comprising the above-mentioned nitrogen-containing heterocyclic organic compound.

A mixture comprising an organic compound H1 and an organic functional material H2, the H1 the organic compound containing the nitrogen heterocycle or the high polymer; the H2 is selected from one or more of hole injection material, hole transport material, electron injection material, electron blocking material, hole blocking material, light emitter and host material.

A composition comprising at least one organic compound as defined above, or a polymer as defined above, or a mixture thereof, and at least one organic solvent.

An organic electronic device comprising a functional layer comprising one of the above organic compounds, or the above high polymers, or mixtures of the above, or combinations of the above.

Has the advantages that: the organic compound according to the present invention has a suitable LUMO orbital level and triplet level, and has good carrier transport ability. The use of the organic compounds according to the invention or the mixtures according to the invention in OLEDs, in particular as host materials for the light-emitting layer, makes it possible to increase the efficiency of the exciton utilization and to increase the efficiency and the lifetime of the relevant devices.

Detailed Description

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

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

In the present invention, when the same substituent is present in multiple times, it may be independently selected from different groups. As shown in the general formula, the compound contains a plurality of R₁Then R is₁Can be independently selected from different groups.

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, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may be further substituted with art-acceptable substituents; 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 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 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.

In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing the term, e.g., "C_1-9Alkyl "refers to an alkyl group containing 1 to 9 carbon atoms, which may be independently at each occurrence C₁Alkyl radical, C₂Alkyl radical, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl radical, C₆Alkyl radical, C₇Alkyl radical, C₈Alkyl or C₉An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-butylcyclohexyl, 2-butylheptyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-tert-butylhexyl, 2-butylhexyl, or a, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantane and the like.

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.

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

"amino" refers to a derivative of ammonia having the formula-N (X)₂Wherein each "X" is independently H, substituted or unsubstitutedSubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted heterocyclic groups, and the like. Non-limiting types of amine groups include-NH₂-N (alkyl)₂NH (alkyl), -N (cycloalkyl)₂NH (cycloalkyl), -N (heterocyclyl)₂NH (heterocyclyl), -N (aryl)₂NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.

In the present invention, "+" attached to a single bond represents a connection or a fusion site; (ii) a

Indicating a bond break.

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.

To represent

Can be combined with

The optional position on the middle benzene ring forms a combined ring.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy level ET, HOMO, and 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 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 Gaussian 03W (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.

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

The invention relates to a nitrogen heterocyclic ring-containing organic compound, which has a structural general formula shown in formula (1):

wherein,

x is independently selected from CR at each occurrence₁Or N; preferably, X is independently selected from CR at each occurrence₁；

Y₁Selected from the group consisting of CR₂R₃、NR₄O or S;

Y₂selected from single bond, CR₂R₃O or S;

R₁to R₄Each occurrence is independently selected from a hydrogen atom, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, a CF group, a hydroxyl group, a nitro group, a hydroxyl group, a sulfo group or an isothiocyanate group₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₁With or without a ring of interconnects.

In one embodiment, the substituted finger of the present invention is R₁And (4) substitution.

In one embodiment, the compound has a general structural formula selected from any one of formulas (2-1) to (2-4):

in one embodiment, the organic compound according to the invention, adjacent R₁Do not form a ring with each other.

In another embodiment, at least two adjacent X's are selected from CR' s₁And the two adjacent R₁Are connected to each other to form any one of cyclic structures shown as (A-1) to (A-4):

wherein:

X₁each occurrence is independently selected from N or CR₅(ii) a Preferably, X₁Each occurrence is independently selected from CR₅；

Y₃Selected from O, S, S ═ O, SO₂、NR₆、PR₆、CR₆R₇Or SiR₆R₇；

R₅-R₇At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

denotes the fusion site.

Further, (A-1) to (A-4) are selected from the following groups:

further, the structural general formula of the compound is selected from any one of formulas (3-1) to (3-7):

in one embodiment, the compound is selected from any one of formulas (4-1) - (4-7):

wherein: r₁And R₄Selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 5 to 40 ring atoms.

In one embodiment, at least two adjacent X in formulas (4-1) - (4-7) are selected from CR₁And the two adjacent R₁Are connected to each other to form any one of the cyclic structures shown by (A-1) to (A-4).

In one embodiment, at least two pairs of two adjacent X's in formulas (4-1) - (4-7) are selected from CR₁And is adjacent to R₁Are connected to each other to form any one of the cyclic structures shown by (A-1) to (A-4).

Further, the compound is selected from any one of the following general formulae (5-1) to (5-6):

in one embodiment, the compound according to the invention, at least one R₁Or R₄Any one selected from (B-1) to (B-3):

wherein:

L₁represents a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms;

X₂at each occurrence, is independently selected from N or CR₈；X₂When present multiple times, at least one X₂Is selected from N;

Y₄selected from NR₉、CR₉R₁₀、SiR₉R₁₀、O、S、S(＝O)₂Or S (═ O);

R₈-R₁₀each occurrence is independently selected from H, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, a CF group, a hydroxyl group, or a hydroxyl group, a₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₈With or without a ring of interconnects.

Further, (B-1) to (B-3) are selected from any one of the following groups:

in one embodiment, R in formula (4-1)₄Selected from any one of (B-1) to (B-3);

in one embodiment, R in formulas (4-2) - (4-7)₁Selected from any one of (B-1) to (B-3); and X is selected from CR₁，R₁Selected from H or are connected with each other in a ring form to form a ring structure shown as (A-1) to (A-4).

In one embodiment, R in formulas (5-1) - (5-6)₁Is selected from any one of (B-1) to (B-3).

In one embodiment, adjacent R in formula (1)₁When not forming a ring with each other, at least one R₁Or R₄Is selected from any one of (B-1) to (B-3).

Preferably, the compound according to the invention, at least one R₁Or R₄Any one selected from the following groups:

specific examples of the organic compound represented by the general formula (1) according to the present invention are listed below, but not limited thereto:

and the H atom of the above structure may be further substituted.

The 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 preferred embodiment, the 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, a compound according to the present invention needs to have a relatively suitable resonance factor f (S1) to facilitate the transfer of excitons from host to guest, and to improve the light emission 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, a compound according to the invention requires a more suitable 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 compounds according to the invention are used as host materials, suitable Δ HOMO and Δ LUMO are required.

In certain preferred embodiments, the compound according to the invention,. DELTA.HOMO, i.e., (. 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 invention also relates to a mixture comprising an organic functional material H1, H1 being selected from the compounds mentioned above, and at least one further 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 this 3 patent document being 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 more preferred embodiment, the mixtures according to the invention, where H1 has a Δ LUMO ≧ 0.1eV, preferably ≧ 0.2eV, more preferably ≧ 0.3 eV.

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 more preferred embodiment, the mixtures according to the invention, where H2 has a. DELTA. HOMO ≧ 0.1eV, preferably ≧ 0.25eV, particularly 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 levels of the triplet states of H1, LUMO (H2), HOMO (H2) and ET (H2) are the lowest unoccupied orbital, the highest occupied orbital, the energy levels of the triplet states of H2, respectively, more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (493H 1)) ≦ min (ET (H1), ET (H2)). more preferably ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H2)) ≦ ET (H1)_T(H1),E_T(H2))-0.1eV；

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

In a preferred embodiment, the organic mixture wherein the molar ratio of H1 to H2 is from 2: 8 to 8: 2; 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 organic 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 organic 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 organic 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 compound according to the invention and a luminescent material selected from singlet emitters, triplet emitters or TADF emitters.

In certain embodiments, the mixture comprises at least one organic compound according to the invention and a singlet emitter in which the singlet emitter is present in an amount of less than or equal to 10 wt.%, preferably less than or equal to 9 wt.%, more preferably less than or equal to 8 wt.%, particularly preferably less than or equal to 7 wt.%, most preferably less than or equal to 5 wt.%.

In a particularly preferred embodiment, the mixture comprises at least one organic compound 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 a further preferred embodiment, the mixture comprises at least one compound according to the invention, a triplet emitter and a host material. In such embodiments, the 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 compound 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, said mixture, said H2 is selected from the group consisting of compounds represented by the following general formula (5):

wherein:

when R is₉Independently at each occurrence, is selected from the group consisting of structural formula (5-1) or a hydrogen atom, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a silyl group, or a ketone group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl, nitro, alkenyl, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; adjacent R₉Are connected with each other to form a ring or not to form a ring;

and R is₉At least one of them is selected from the knotsFormula (5-1);

Ar₃-Ar₄each independently selected from a substituted or unsubstituted aromatic or 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 or heteroaryl group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring group having 5 to 30 ring atoms;

ar is₃，Ar₄，L₂Any two of which may be interconnected to form a ring.

Further, the H2 is selected from compounds shown in the following general formula (6-1) or (6-2):

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 compounds according to the 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 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, most preferably 1200g/mol or more.

In other embodiments, the 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 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 at least 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 contain 0.01 to 10 wt% of the compound or polymer or mixture according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, and most preferably 0.25 to 3 wt%.

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 a use of the 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 (fets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present invention, the 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 compound, polymer or mixture as described above. Generally, such organic electronic devices comprise at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one 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 a compound or mixture or polymer as described above or prepared from a composition as described above.

In certain preferred embodiments, the electroluminescent device comprises a compound as described above in the light-emitting layer, or comprises a compound as described above and a phosphorescent light-emitting material, or comprises a compound as described above and a host material, or comprises a 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 of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 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

1. Synthesis of Compounds

EXAMPLE 1 Synthesis of Compound 1

(1) Synthesis of intermediates 1 to 3: compound 1-1(10.0g), 1-2(4.7g), cuprous iodide (3.8g), potassium carbonate (8.3g), trans 1, 2-cyclohexanediamine (6.8g) were added to 200ml of dry toluene; stirring was carried out at 110 ℃ for 6h under a nitrogen atmosphere. And cooling, carrying out suction filtration, washing the filtrate with water, separating liquid, and recrystallizing to obtain an intermediate 1-3. Ms (asap): 655.58.

(2) synthesis of Compound 1: 1-3(8.5g) was dissolved in 150ml of dry DMAC and palladium acetate (0.44g), P (Cy) were added₃·HBF₄(1.5g) and cesium carbonate (16.9g) were reacted at 140 ℃ for 4 hours in a nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, the remaining reaction solution was poured into a large amount of water and filtered, and the obtained solid was subjected to column chromatography and recrystallization to obtain compound 1. Ms (asap): 582.67.

example 2 synthesis of compound 2:

(1) synthesis of intermediate 2-2: compound 2-1(5.0g), pinacol diboron (5.7g), Pd (dppf) Cl₂(0.1g) and potassium acetate (4.1g) were added to 100ml of dried 1, 4-dioxane; stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, filtering, removing the solvent from the filtrate by rotary evaporation, and recrystallizing to obtain the intermediate 2-2. Ms (asap): 290.95.

(2) synthesis of intermediates 2 to 4: 2-2(4.5g), 2-3(4.2g), Pd (PPh)₃)₄(0.1g) and potassium carbonate (4.3g) were added to a mixed solvent of 1, 4-dioxane/water (60ml/15 ml); stirred at 85 ℃ for 6h under nitrogen atmosphere. After cooling, filtering, removing the solvent from the filtrate by rotary evaporation, and recrystallizing to obtain the intermediate 2-4. Ms (asap): 396.25.

(3) synthesis of intermediates 2 to 6: intermediates 2-4(5.5g), 2-5(3.9g) were dissolved in 100ml dry DMF and cesium carbonate (9.1g) was added and stirred at elevated temperature to 140 ℃ for 6h under a nitrogen atmosphere. After cooling, the filtrate was poured into a large amount of water to precipitate a solid. And (4) carrying out suction filtration, and recrystallizing the obtained solid to obtain an intermediate 2-6. Ms (asap): 659.61.

synthesis of compound 2 the synthesis of compound 1 was referenced, except that intermediates 1-3 were replaced with intermediates 2-6. Ms (asap): 586.70.

EXAMPLE 3 Synthesis of Compound 3

(1) Synthesis of intermediate 3-2 reference was made to the synthesis of 2-6, except intermediate 2-5 was replaced with intermediate 3-1. Ms (asap): 749.70.

(2) synthesis of compound 3 reference was made to the synthesis of compound 1 except that 1-3 was replaced with intermediate 3-2. Ms (asap): 676.78.

EXAMPLE 4 Synthesis of Compound 4

(1) Synthesis of intermediate 4-3: compound 4-1(5.0g), 4-2(4.4g), cuprous iodide (5.7g), potassium phosphate (6.3g), trans 1, 2-cyclohexanediamine (5.2g) were added to 150ml of dry toluene, and stirred at 100 ℃ for 5 hours under a nitrogen atmosphere. Cooling, filtering, removing solvent from filtrate by rotary evaporation, and performing column chromatography to obtain intermediate 4-3. Ms (asap): 504.76.

(2) synthesis of intermediates 4-4: dried 4-3(10mmol) was dissolved in dry THF (80mL), cooled to 0 deg.C under a nitrogen atmosphere, and a solution of methylmagnesium bromide (20mmol) was slowly added dropwise and stirred for 2 hours. The unreacted methylmagnesium bromide was carefully quenched with saturated ammonium chloride solution at 0 ℃. And washing the separated liquid with water and extracting. The organic phase was spin dried and the resulting solid was dissolved in a mixed solution of acetic acid/hydrochloric acid (volume ratio 3:1,60ml) and stirred at 80 ℃ for 4 h. After cooling, the reaction was slowly poured into a large amount of water and filtered. And repeatedly washing the filter cake for several times by water, sodium bicarbonate solution and water in sequence, and then recrystallizing to obtain an intermediate 4-4. Ms (asap): 486.79.

(3) synthesis of intermediates 4 to 6: mixing 4-4(4.8g), 4-5(4.0g), Pd (PPh)₃)₄(0.1g) and potassium carbonate (2.8g) were added to a mixed solvent of 1, 4-dioxane/water (80ml/20 ml); stirring was carried out at 80 ℃ for 6h under a nitrogen atmosphere. Cooling, suction filtering, rotary evaporating filtrate to remove solvent, and recrystallizing to obtain intermediate 4-6. Ms (asap): 688.23.

(4) synthesis of Compound 4: compound 4-6(8.0g) was dissolved in 150ml of dried DMAC, and palladium acetate (0.44g), P (Cy) were added₃·HBF₄(1.5g) and cesium carbonate (7.6g) were reacted at 140 ℃ for 4 hours in a nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, the remaining reaction solution was poured into a large amount of water and filtered, and the filter cake was subjected to column chromatography and recrystallization to obtain compound 4. Ms (asap): 651.77.

EXAMPLE 5 Synthesis of Compound 5

(1) Synthesis of intermediate 5-3 reference was made to the synthesis of 4-3, except that 4-1 was replaced with 5-1 and 4-2 was replaced with 5-2. Ms (asap): 524.88.

(2) synthesis of intermediates 5 to 4: adding the compound 5-3(10.0g), phosphorus pentoxide (5.9g) and 60mL of trifluoromethanesulfonic acid into a 150mL three-necked bottle, stirring at room temperature for 24 hours, finishing the reaction, slowly inverting the reaction solution into 300mL of ice water, performing suction filtration, washing filter residues with water, sodium bicarbonate aqueous solution and water for several times, collecting the filter residues, drying, placing the filter residues into 50mL of pyridine, performing reflux reaction for 12 hours, cooling to room temperature, extracting with dichloromethane for 3 times, collecting organic solution, mixing with silica gel, and performing column chromatography for purification. Ms (asap): 492.83.

(3) synthesis of intermediates 5 to 5: compound 5-4(8.5g), pinacol ester diboron (4.4g), Pd (dppf) Cl₂(0.1g) and potassium acetate (3.4g) were added to 100ml of dried 1, 4-dioxane; stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. Cooling, suction filtering, rotary evaporating filtrate to remove solvent, and recrystallizing to obtain intermediate 5-5. Ms (asap): 539.90.

(4) synthesis of intermediates 5 to 7: mixing compounds 5-5(7.5g), 5-6(3.3g), Pd (PPh)₃)₄(0.1g) and potassium carbonate (4.9g) were added to a mixed solvent of 1, 4-dioxane/water (160ml/20ml), and the mixture was heated to 100 ℃ under a nitrogen atmosphere and stirred for 8 hours. Cooling, suction filtering, rotary evaporating filtrate to remove solvent, and recrystallizing to obtain intermediate 5-7. Ms (asap): 684.27.

(5) synthesis of Compound 5 reference was made to the synthesis of Compound 4, except that 4-6 was replaced with 5-7. Ms (asap): 647.81.

EXAMPLE 6 Synthesis of Compound 6

(1) Synthesis of intermediate 6-3: mixing the compound 6-1(8.0g), 6-2(3.8g), Pd (dba)₂(0.1g), tri-tert-butylphosphine (0.18g), and sodium tert-butoxide (2.0g) were added to 150ml of dry toluene, and stirred at 80 ℃ for 6 hours under a nitrogen atmosphere. After cooling, filtering, washing the filtrate with water, separating the liquid, removing the solvent by rotary evaporation of an organic phase, and recrystallizing to obtain an intermediate 6-3. Ms (asap): 698.61.

(2) synthesis of Compound 6 reference was made to the synthesis of Compound 1, except that 1-3 was replaced with 6-3. Ms (asap): 625.69.

EXAMPLE 7 Synthesis of Compound 7

(1) Synthesis of intermediate 7-3 reference was made to the synthesis of 2-4, except that 2-2 was replaced with 7-2 and 2-3 was replaced with 7-1. Ms (asap): 553.50.

(2) synthesis of intermediate 7-5 reference was made to the synthesis of 6-3, except that 6-1 was replaced with 7-3 and 6-2 was replaced with 7-4. Ms (asap): 740.75.

(2) synthesis of Compound 7 reference was made to the synthesis of Compound 1 except that 1-3 was replaced with 7-5. Ms (asap): 667.83.

EXAMPLE 8 Synthesis of Compound 8

(1) Synthesis of intermediate 8-2 reference was made to the synthesis of 5-5, except that 5-4 was replaced with 8-1. Ms (asap): 459.40.

(2) synthesis of intermediate 8-3 reference was made to the synthesis of 5-7, except that 5-5 was replaced with 8-2 and 5-6 was replaced with 2-3. Ms (asap): 564.69.

(3) synthesis of intermediates 8-5 reference was made to the synthesis of 2-6, except that 2-5 was replaced with 8-3 and 2-4 was replaced with 8-4. Ms (asap): 709.67.

(3) synthesis of Compound 8 reference was made to the synthesis of Compound 1, except that 1-3 was replaced with 8-5. Ms (asap): 636.76.

EXAMPLE 9 Synthesis of Compound 9

(1) Synthesis of intermediate 9-2 reference was made to the synthesis of 4-3, except that 4-1 was replaced with 9-1. Ms (asap): 686.02.

(2) synthesis of intermediate 9-3 reference was made to the synthesis of 4-4, except that 4-3 was replaced with 9-2. Ms (asap): 668.05.

(3) synthesis of intermediate 9-4 reference was made to the synthesis of 5-5, except that 5-4 was replaced with 9-3. Ms (asap): 715.12.

(4) synthesis of intermediate 9-6 reference was made to the synthesis of 5-7, except that 5-5 was replaced with 9-4 and 5-6 was replaced with 9-5. Ms (asap): 833.41.

(5) synthesis of compound 9 reference was made to the synthesis of compound 4 except that 4-6 was replaced with 9-6. Ms (asap): 796.95.

EXAMPLE 10 Synthesis of Compound 10

(1) Synthesis of intermediate 10-2 reference was made to the synthesis of 5-5, except that 5-4 was replaced with 10-1. Ms (asap): 549.48.

(2) synthesis of intermediate 10-4 reference was made to the synthesis of 5-7, except that 5-5 was replaced with 10-2 and 5-6 was replaced with 10-3. Ms (asap): 627.75.

(3) synthesis of intermediate 10-5 reference was made to the synthesis of 2-6, except that 2-5 was replaced with 10-4 and 2-4 was replaced with 8-4. Ms (asap): 772.73.

(4) synthesis of Compound 10 reference was made to the synthesis of Compound 1 except that 1-3 was replaced with 10-5. Ms (asap): 699.81.

EXAMPLE 11 Synthesis of Compound 11

(1) Synthesis of intermediate 11-2 reference was made to the synthesis of 2-6, except that 2-5 was replaced with 11-1. Ms (asap): 765.76.

(2) synthesis of Compound 11 reference was made to the synthesis of Compound 1 except that 1-3 was replaced with 11-2. Ms (asap): 692.84.

EXAMPLE 12 Synthesis of Compound 12

(1) Synthesis of intermediate 12-2: 12-1(8.0g) and NaH (1.01g) were dissolved in 200ml of dry DMF and stirred at room temperature for 1h under a nitrogen atmosphere; then 12-2(9.4g) was added under nitrogen atmosphere, and the mixture was stirred for 12 hours while being warmed to 80 ℃. After cooling, ethanol is slowly added at 0 ℃ to remove the unreacted NaH, then most of the solvent is removed by reduced pressure distillation, and the intermediate 12-3 is obtained by extraction, water washing, liquid separation, column chromatography and recrystallization. Ms (asap): 501.39.

(2) synthesis of intermediate 12-4 reference was made to the synthesis of 1-3, except that 1-1 was replaced with 12-3. Ms (asap): 656.57.

(3) synthesis of Compound 12 reference was made to the synthesis of Compound 1 except that 1-3 was replaced with 12-4. Ms (asap): 583.65.

EXAMPLE 13 Synthesis of Compound 13

(1) Synthesis of intermediate 13-1 reference was made to the synthesis of 2-4, except that 2-3 was replaced with 10-3. Ms (asap): 369.22.

(2) synthesis of intermediate 13-3 reference was made to the synthesis of 2-6, except that 2-4 was replaced with 13-1 and 2-5 was replaced with 13-2. Ms (asap): 732.71.

(3) synthesis of Compound 13 reference was made to the synthesis of Compound 1 except that 1-3 was replaced with 13-3. Ms (asap): 659.79.

2. device preparation and detection

Device example 1

The device structure is ITO/HATCN/HTM/host material (compound 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, 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. in the order of 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.

The preparation of the remaining OLED devices was referenced 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.

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, is calculated relative to comparative device example 1 (corresponding to comparative material example 1), i.e. with the lifetime of comparative device example 1 being 1 and the external quantum efficiency being 100.

Table 1: OLED device Performance comparison

Device examples 1-13 have significantly higher out-of-device quantum efficiencies and lifetimes than comparative device example 1 (corresponding to comparative example 1). The material disclosed by the invention has a condensed 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. In addition, the material of the invention has a larger conjugated system than the comparative material, thereby having better charge transport capability and stability than the comparative material. Among them, the device lifetimes of device example 3, device example 8 to device example 11, and device example 13 are significantly higher than those of the other single-host examples (corresponding to device example 1 to device example 2, device example 4 to device example 7, and device example 12), because the compounds used in these examples have a larger fused ring system and better stability, and the transport capability of carriers between molecules is better. Device example 14 (corresponding to a mixture of material 4: H2-1 in a mass ratio of 1: 1) and device example 15 (corresponding to a mixture of material 8: H2-2 in a mass ratio of 1: 1) using the mixture of the present invention as a co-host had the highest device lifetime and external quantum efficiency (EQE both exceeding 25%) because the co-host had relatively more balanced hole/electron transport properties, 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 organic compound containing a nitrogen heterocycle is characterized in that the structural general formula is shown as formula (1):

wherein,

x is independently selected from CR at each occurrence₁Or N;

Y₁selected from the group consisting of CR₂R₃、NR₄O or S;

Y₂selected from single bond, CR₂R₃O or S;

2. The nitrogen-containing heterocyclic organic compound according to claim 1, wherein adjacent R is₁Do not form a ring with each other.

3. The nitrogen-containing heterocyclic organic compound according to claim 1, wherein at least two adjacent X are selected from CR₁And the two adjacent R₁Are connected to each other to form any one of cyclic structures shown as (A-1) to (A-4):

wherein:

X₁each occurrence is independently selected from N or CR₅；

denotes the fusion site.

4. The nitrogen-containing heterocyclic organic compound according to claim 3, characterized in that the general structural formula of the compound is selected from any one of formulae (3-1) to (3-7):

5. the nitrogen-containing heterocyclic organic compound according to claim 1, characterized in that the general structural formula of the compound is selected from any one of formulae (4-1) to (4-7):

6. the nitrogen-containing heterocyclic organic compound according to claim 1, characterized in that the general structural formula of the compound is selected from any one of formulae (5-1) to (5-6):

7. the nitrogen-containing heterocyclic organic compound according to any one of claims 1 to 6, wherein at least one R is₁Or R₄Any one selected from the following groups:

wherein:

X₂at each occurrence, is independently selected from N or CR₈；

R₈-R₁₀independently at each occurrence, selected from H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms,or alkoxycarbonyl having 2 to 20C atoms or aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₈With or without a ring of interconnects.

8. The nitrogen-containing heterocyclic organic compound according to claim 7, wherein at least one R₁Or R₄Any one selected from the following groups:

9. a mixture comprising an organic compound H1 and an organic functional material H2, wherein H1 is selected from the group consisting of the nitrogen-containing heterocyclic organic compounds according to any one of claims 1 to 8; the H2 is selected from one or more of hole injection material, hole transport material, electron injection material, electron blocking material, hole blocking material, light emitter and host material.

10. The mixture of claim 9, wherein H2 is selected from the group consisting of compounds represented by the following formula (5):

wherein:

when R is₉Each occurrence is independently selected from the group consisting of formula (5-1) or a hydrogen atom, or D, or a straight chain alkyl, alkoxy or thioalkane having 1 to 20C atomsOxy, or branched or cyclic alkyl, alkoxy or 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, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, alkenyl, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; adjacent R₉Are connected with each other to form a ring or not to form a ring;

and R is₉At least one of them is selected from the structural formula (5-1);

ar is₃，Ar₄，L₂Any two of which can be connected with each other to form a ring;

indicating a bond break.

11. The mixture according to claim 9, wherein H2 is selected from any one of the following compounds, and ring hydrogens may be optionally substituted:

12. a composition comprising a nitrogen-containing heterocyclic organic compound according to any one of claims 1 to 8, or a mixture according to any one of claims 9 to 11, and at least one organic solvent.

13. An organic electronic device comprising a functional layer comprising the nitrogen-containing heterocyclic organic compound of any one of claims 1 to 8, or the mixture of any one of claims 9 to 11, or prepared from the composition of claim 12.