CN114751940A

CN114751940A - Binuclear iridium complex of pyrazole auxiliary ligand and application thereof

Info

Publication number: CN114751940A
Application number: CN202210292603.8A
Authority: CN
Inventors: 杨曦; 张曲
Original assignee: Guangzhou Zhuoguang Technology Co ltd
Current assignee: Guangzhou Zhuoguang Technology Co ltd
Priority date: 2022-03-23
Filing date: 2022-03-23
Publication date: 2022-07-15
Anticipated expiration: 2042-03-23
Also published as: CN114751940B

Abstract

The invention relates to a binuclear iridium complex of a pyrazole auxiliary ligand and application thereof. In a binuclear complex structure, a single auxiliary ligand simultaneously coordinates two heavy metal atoms Ir, and a bridging ligand group can effectively shorten the Ir-Ir atomic distance, so that the light-emitting peak of a molecule is red-shifted, and the light-emitting wavelength of the molecule reaches 640-650 nm; the dual-core structure based on ligand bridging has more stable molecular structure and good thermal stability, so that the prepared device has high stability, and the service life of the prepared organic light-emitting diode device is also long.

Description

Binuclear iridium complex of pyrazole auxiliary ligand and application thereof

Technical Field

The invention relates to the field of luminescent materials, in particular to a binuclear iridium complex of a pyrazole auxiliary ligand and an organic electronic device.

Background

Currently, the lighting display technology has been developed to the third generation display technology, Organic Light Emitting Diodes (OLEDs), and the OLEDs have many advantages, such as: the self-luminous flexible substrate can be self-luminous without being limited by a backlight source, has high light output rate, can realize full-color display in a spectrum adjustable range from red light to blue light, has a simple structure, and can be prepared on a flexible substrate. The conventional OLEDs are classified into fluorescent OLEDs and phosphorescent OLEDs according to the classification of the electroluminescent material of the core. Compared with fluorescent OLEDs (the theoretical luminous efficiency is 25 percent at most), the organic electrophosphorescent material can simultaneously utilize singlet excitons and triplet excitons, and the theoretical luminous quantum efficiency can reach 100 percent, so the organic electrophosphorescent material becomes a hotspot in the field of electroluminescent research. Among them, phosphorescent metal complexes, such as iridium complexes, are very effective in enhancing cross-change of electron spin states between singlet excited states and triplet excited states due to strong spin-orbit coupling (ISC) of heavy metal atoms thereof, and thus iridium complexes are good candidates as dopants of light emitting layers of Organic Light Emitting Devices (OLEDs) as classical phosphorescent materials. Over the past decade, people have achieved some success on the way this technology goes to highly profitable commercialization, for example OLEDs have found application in displays for smart phones, televisions and digital cameras.

Iridium complexes, such as bis (2-benzothienyl) pyridine-N, C3') (acetylacetone) iridium, bis [2- (2-benzothienyl) pyridine-N, C3] (acetylacetinato) iridium (iii) [ Btp2Ir (acac) ] and the like, which are red light emitting materials, have been commercially used, and their emission wavelengths are generally 600 to 620nm, which allows DCI-P3 color gamut coverage.

Document 1: chinese patent CN107459535A, polysubstituted quinoline coordinated iridium heterocomplex, preparation method and application 2017.12. Disclosed is a polysubstituted quinoline coordinated iridium complex, the light-emitting wavelength of which is 600-630 nm.

However, as the requirement of display effect is higher, BT2020 color gamut coverage needs to be achieved, or deep red light illumination technology needs to be achieved, and a deep red light material with longer light emitting wavelength is needed.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a binuclear iridium complex of a pyrazole auxiliary ligand and application thereof in a light-emitting device.

In order to realize the purpose of the invention, the specific technical solution is as follows:

a binuclear iridium complex of a pyrazole auxiliary ligand, which is shown as a general formula (I):

wherein the content of the first and second substances,

each occurrence, identically or differently, is selected from any one of the following structures:

wherein: r₁-R₁₁Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, a substituted or unsubstituted straight-chain alkyl or alkoxy group having from 1 to 20C atoms, a substituted or unsubstituted branched-chain alkyl or alkoxy group having from 3 to 20C atoms, a substituted or unsubstituted cycloalkanyl group having from 3 to 20C atoms, a substituted or unsubstituted aromatic group having from 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 30 ring atoms, or a combination of these groups;

the dotted line represents

A site of attachment to Ir.

Correspondingly, the invention also provides a mixture, which comprises the binuclear iridium complex of the pyrazole auxiliary ligand and at least one organic functional material, wherein the organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting object material, a light-emitting host material or an organic dye.

Correspondingly, the invention also provides a composition which comprises the dinuclear iridium complex of the pyrazole auxiliary ligand or the mixture and at least one organic solvent.

Correspondingly, the invention also provides an organic electronic device which comprises at least one functional layer, wherein the functional layer contains the binuclear iridium complex of the pyrazole auxiliary ligand or the mixture, or the functional layer is prepared from the composition.

The principle of the invention is as follows: under the binuclear complex structure, a single auxiliary ligand coordinates two heavy metal atoms Ir at the same time, and a bridging ligand group can effectively shorten the Ir-Ir atomic distance so that the luminous peak of the molecule is red-shifted.

Compared with the prior art, the invention has the following remarkable advantages:

the binuclear iridium complex of the pyrazole auxiliary ligand provided by the invention takes a pyrazole derivative as an auxiliary bridging ligand, effectively shortens the Ir-Ir atomic distance, enables the light-emitting peak of a molecule to be red-shifted, and is applied to an OLED light-emitting device, and the light-emitting wavelength of the binuclear iridium complex reaches 640-650 nm;

the binuclear iridium complex of the pyrazole auxiliary ligand is based on a ligand bridged binuclear structure, has a more stable molecular structure and good thermal stability, and leads to high stability of a prepared device, so that the binuclear iridium complex has quite high device service life, and can be effectively applied to wide color gamut coverage of BT2020 in a display technology and requirements of deep red light illumination (such as automobile tail lamps).

Drawings

FIG. 1 is a schematic diagram of the OLED structure of the present invention.

Wherein 101 is a substrate; 102 is an anode; 103 is a hole injection layer; 104 is a hole transport layer; 105 is a light emitting layer; 106 is an electron transport layer; 107 is an electron injection layer; 108 is a cathode.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto. The measurement methods not described in detail in the present invention are all conventional in the art.

The term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or" and/or ", it should be understood that in this application, the technical solutions unquestionably include the technical solutions all connected by" logical and ", and also unquestionably include the technical solutions all connected by" logical or ". For example, "A and/or B" includes A, B and A + B. For example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all embodiments using a "logical or" connection), any and all combinations of A, B, C, D, i.e., any two or any three of A, B, C, D, and four combinations of A, B, C, D (i.e., all embodiments using a "logical and" connection).

In the present invention, "substituted" means that one or more hydrogen atoms in a substituent are substituted with a substituent.

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

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.

"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthyl, triphenylene, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. < 10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: thienyl, furyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-diazonaphthyl, phenanthridinyl, primidinyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

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 encompassing this term, such as "C1-9 alkyl" refer to an alkyl group containing from 1 to 9 carbon atoms, which at each occurrence can be, independently of each other, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. 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, 2-ethylpentyl, 4-methyl-2-pentyl, n-methylhexyl, 2-ethylhexyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-ethylhexyl, 2-ethyloctyl, 2-ethylhexyl, 2, tert-ethyloctyl, 2-ethylhexyl, tert-butylhexyl, 2-butylhexyl, n-octyl, tert-butyl, 2-pentyl, n-pentyl, tert-pentyl, cyclohexyl, 2-pentyl, cyclohexyl, 2, or a, cyclohexyl, 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, and the like.

The term "alkoxy" refers to a group of the structure "-O-alkyl", i.e. an alkyl group as defined above is attached to other groups via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH3 or-OMe), ethoxy (-O-CH2CH3 or-OEt) and t-butoxy (-O-C (CH3)3 or-OtBu).

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

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

The terms "combination thereof", "any combination thereof", "combination of groups", "combination" and the like as used herein include all suitable combinations of any two or more of the listed groups.

In the present invention, "further", "still further", "specifically" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of the present invention.

In the present invention, "optionally", "optional" and "optional" refer to the presence or absence, i.e., to any one of two juxtapositions selected from "present" and "absent". If multiple optional parts appear in one technical scheme, if no special description exists, and no contradiction or mutual constraint relation exists, each optional part is independent.

In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.

A binuclear iridium complex of a pyrazole auxiliary ligand has the following molecular structural formula:

wherein the content of the first and second substances,

wherein: r is₁-R₁₁Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, a substituted or unsubstituted straight or branched alkyl group having 1 to 20C atoms, a substituted or unsubstituted branched alkyl or branched alkoxy group having 3 to 20C atoms, a substituted or unsubstituted cycloparaffin group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a combination of these groups;

the dotted line represents

A site of attachment to Ir.

In one embodiment, one or more H of the dinuclear iridium complexes of the pyrazole ancillary ligands are substituted with D.

In one embodiment, R₁-R₁₁Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, a substituted or unsubstituted straight-chain alkyl or alkoxy group having 1 to 10C atoms, a substituted or unsubstituted branched-chain alkyl or alkoxy group having 3 to 10C atoms, a substituted or unsubstituted cycloalkanyl group having 3 to 10C atoms, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.

Preferably, said "substituted or unsubstituted" means that the group may be unsubstituted or substituted with one or more substituents selected from D, cyano, isocyano, nitro or halogen, alkyl containing 1-20C atoms, heterocyclyl containing 3-20 ring atoms, aromatic containing 6-20 ring atoms, heteroaromatic containing 5-20 ring atoms, or a combination of these groups; further, the substituents are selected from D, cyano, isocyano, nitro or halogen, alkyl containing 1-10C atoms, heterocyclyl containing 3-10 ring atoms, aromatic containing 6-10 ring atoms, heteroaromatic containing 6-10 ring atoms, or a combination of these groups.

In one embodiment, R₁-R₁₁Independently at each occurrence is selected from H, D, a straight chain alkyl group having 1 to 10C atoms substituted with one or more D, a branched alkyl group having 3 to 10C atoms substituted with one or more D, or a group A:

wherein: r₁₂Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, straight chain alkyl having 1 to 10C atoms substituted with one or more D, branched alkyl having 3 to 10C atoms substituted with one or more D, or phenyl;

denotes the attachment site.

In a particular embodiment of the present invention,

in an implementationIn the example shown in the figure, the water-soluble polymer,

each occurrence is selected from the same structure.

Specific examples of the pyrazole-assisted coordinated binuclear iridium complex according to the present invention include, but are not limited to, the following:

in one embodiment, the pyrazole-assisted coordinated binuclear iridium complex can be used as an organic functional material in a functional layer of an organic electronic device, particularly an OLED device. The organic functional material may be, 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), a light emitting guest material (guest Emitter), a light emitting Host material (Host Emitter), and an organic dye.

In one embodiment, the one pyrazole-assisted coordination binuclear iridium complex of the present application is used in a light-emitting layer, and preferably, the one pyrazole-assisted coordination binuclear iridium complex of the present application is used as a guest material of the light-emitting layer in the light-emitting layer.

In a specific embodiment, the organic compounds according to the present application are used in the light-emitting layer as red light-emitting guest materials.

The present application further provides a mixture comprising at least one pyrazole-assisted coordinative binuclear iridium complex as described above and at least one further organic functional material. The other organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting guest material, a light emitting host material and an organic dye. Wherein the luminophores are selected from singlet state luminophores (fluorescent luminophores) or triplet state luminophores (phosphorescent luminophores) grade organic thermal excitation delayed fluorescence materials (TADF materials). Details of various organic functional materials are described in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of this 3 patent document being hereby incorporated by reference. It is understood that the other organic functional material may be a small molecule organic material and a high polymer material.

In an embodiment, the further organic functional material is selected from host materials. Wherein the weight percentage of the pyrazole-assisted coordination binuclear iridium complex in the mixture is more than 0 and less than or equal to 25 wt%, preferably more than 0 and less than or equal to 15 wt%, more preferably more than 0 and less than or equal to 5 wt%, and further more preferably more than 0 and less than or equal to 2 wt%.

The present application also relates to a composition comprising at least one pyrazole-assisted coordinated binuclear iridium complex or mixture as described above and at least one organic solvent.

The organic solvent is at least one selected from the group consisting of aromatic or heteroaromatic-based solvents, ester-based solvents, aromatic ketone-based solvents, aromatic ether-based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefinic compounds, borate compounds, and phosphate compounds.

In at least one embodiment, the organic solvent in the composition is selected from aromatic or heteroaromatic-based solvents.

The aromatic or heteroaromatic-based solvent may be selected from, but is 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, and mixtures thereof, At least one of 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, and ethyl 2-furancarboxylate.

The ester-based solvent may be selected from, but is not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particularly, at least one of octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate is preferable.

The aromatic ketone-based solvent may be selected from the group consisting of, but not limited to, 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. Wherein, as an example, the derivative may be selected from at least one of, but not limited to, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, and 2-methylpropiophenone.

The aromatic ether-based solvent may be selected from, but is not limited to, 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxybenzene, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1, 3-dipropylanisole, 1, 2-propenyloxybenzene, 1, 4-dimethoxybenzene, and mixtures thereof, At least one of 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran and ethyl-2-naphthyl ether.

The aliphatic ketone-based solvent may be selected from, but is not limited to, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, and the like; or an aliphatic ether, for example, at least one of 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, and tetraethylene glycol dimethyl ether.

It is to be understood that the organic solvent may be used alone or as a mixed solvent of two or more organic solvents.

In one embodiment, the composition of the present application comprises at least one pyrazole-assisted coordinated binuclear iridium complex or mixture as described above, and at least one organic solvent, and may further comprise another organic solvent.

The another organic solvent may be selected from, but not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, 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 (DMSO), tetrahydronaphthalene, decalin, and indene.

In one embodiment, organic solvents suitable for the present application are those having Hansen (Hansen) solubility parameters within the following ranges:

delta d (dispersion force) at 17.0MPa^1/2-23.2MPa^1/2In the scope, especially in18.5MPa^1/2-21.0MPa^1/2Within the range;

delta p (polar force) is 0.2MPa^1/2-12.5MPa^1/2In the range, especially 2.0MPa^1/2-6.0MPa^1/2Within the range;

delta h (hydrogen bonding force) is 0.9MPa^1/2-14.2MPa^1/2In the range, especially at 2.0MPa^1/2-6.0MPa^1/2Within the range.

In one embodiment, the organic solvent is selected with a boiling point in mind, in accordance with the compositions herein. In at least some embodiments, the organic solvent has a boiling point of 150 ℃ or higher; preferably more than or equal to 180 ℃; 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.

It is understood that the organic solvent may be evaporated from the solvent system to form a thin film comprising the organic compound.

In one embodiment, the composition is a solution. In still other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, and the like. The additive may be selected from, but not limited to, at least one of a surface active compound, a lubricant, a wetting agent, a dispersant, a hydrophobizing agent, and a binder.

The composition may also be referred to as an ink.

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

In one embodiment, the surface tension of an ink according to the present application at operating temperature or at 25 ℃ is in the range of about 19dyne/cm to about 50 dyne/cm; more preferably 22dyne/cm to 35 dyne/cm; preferably 25dyne/cm to 33 dyne/cm.

In one embodiment, the viscosity of the ink according to the present application ranges from 1cps to 100cps at operating temperature or 25 ℃; preferably 1cps to 50 cps; more preferably 1.5cps to 20 cps; preferably 4.0cps to 20 cps.

It will be appreciated that inks having the surface tensions and viscosities described above will facilitate ink jet printing.

It will be appreciated that the viscosity of the ink can be adjusted in different ways, such as by appropriate solvent selection and concentration of the functional material in the ink. Inks containing organic compounds according to the present application can facilitate one to adjust the printing ink in the appropriate range according to the printing method used. The composition of the present application comprises the organic compound or mixture in an amount of 0.01 to 15 wt%, preferably 0.1 to 10 wt%, more preferably 0.2 to 5 wt%, most preferably 0.25 to 3 wt%.

The application also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices. In one embodiment, the composition is used to prepare organic electronic devices by a printing or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, jet printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roll printing, twist roll printing, offset printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred.

The application also relates to the application of the pyrazole-assisted coordinated binuclear iridium complex, the mixture or the composition in the organic electronic device. In one embodiment, the present application provides an organic electronic device comprising at least one functional layer. The functional layer comprises at least one pyrazole-assisted coordinated binuclear iridium complex or mixture as described above, or is prepared from the above-described composition.

Further, the organic electronic device comprises a cathode, an anode and at least one functional layer. The functional layer comprises at least one pyrazole-assisted coordinated binuclear iridium complex or mixture as described above, or is prepared from a composition as described above.

The functional layer may be, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer, an electron blocking layer, an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), or a hole blocking layer. Preferably, the functional layer is a light emitting layer. The luminescent layer comprises at least one pyrazole-assisted coordinated binuclear iridium complex or mixture as described above, or the luminescent layer is prepared from a composition as described above.

In one embodiment, the light-emitting layer includes a light-emitting host material and a light-emitting guest material, and the light-emitting guest material is the above-mentioned binuclear iridium complex or mixture with pyrazole-assisted coordination. Further, the mass ratio of the light-emitting layer guest material to the host material is more than or equal to 25%; further, the mass ratio of the light-emitting layer guest material to the host material is more than or equal to 15%; further, the mass ratio of the light-emitting layer guest material to the host material is greater than or equal to 5%.

The Organic electronic device may be, but is not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like. Particularly preferred are organic electroluminescent devices such as OLEDs, OLEECs, organic light emitting field effect transistors, and the like. More particularly, OLEDs are preferable.

The substrate may be transparent or opaque. 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 also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate without surface defects is particularly desirable. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ℃ or higher, preferably above 200 ℃, more preferably above 250 ℃, and most preferably above 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode is an electrode for injecting holes, and the anode can easily inject holes into the hole injection layer, or the hole transport layer, or the light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. 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 application.

The cathode is an electrode for injecting electrons, and the cathode can easily inject electrons into the electron injection layer, or the electron transport layer, or the light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or the n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for organic electronic devices are possible as cathode materials for organic electronic devices according to the present application. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The hole injection layer is a layer for promoting injection of holes from the anode to the light-emitting layer, and the hole injection material is a material that can proficiently receive holes injected from the positive electrode at a low voltage, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile-hexaazatriphenylene-based organic material, and the like, but are not limited thereto.

The hole transport layer may serve to smoothly transport holes. The hole transport material known in the art for the hole transport layer is suitably a material having high hole mobility, which can receive holes transported from the anode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, HT23, and the like, but are not limited thereto.

The electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, a spiroindoloacridine-based compound or a material known in the art may be used.

Examples of the host material for the light-emitting layer include a condensed aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specifically, examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.

The electron transport layer may serve to smoothly transport electrons. The electron transport material is suitably a material having high electron mobility, which can skillfully receive electrons injected from the negative electrode and transfer the electrons to the light emitting layer. Specific examples thereof may include, but are not limited to: at least one of an Al complex of 8-hydroxyquinoline, a complex comprising Alq3, an organic radical compound, a hydroxyflavone-metal complex, lithium 8-hydroxyquinoline (LiQ), ET24, and a benzimidazole-based compound.

The electron injection layer may be used to smoothly inject electrons. The electron injection material is preferably: has an ability to transport electrons, has an effect of injecting electrons from a negative electrode, and has an excellent effect of injecting electrons into a light-emitting layer or a light-emitting material, prevents excitons generated from the light-emitting layer from moving to a hole-injecting layer, and also has an excellent ability to form a thin film. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, TmPyPB, and the like, but are not limited thereto.

The hole blocking layer is a layer that blocks holes from reaching the negative electrode, and may be generally formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, oxadiazole or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.

The organic electronic device has a light emission wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 640 and 650 nm.

In one embodiment, the organic electronic device described herein is a solution-type organic electronic device, wherein one or more functional layers thereof are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.

The present application also relates to the use of the organic electronic device according to the present application in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, etc.

The application also relates to an electronic device comprising said organic electronic device. The electronic device may be, but is not limited to, a display device, an illumination device, a light source, a sensor, and the like.

The present application will be described in detail with reference to specific examples, which are intended to be part of the present application and are not intended to limit the present application. The present application is not limited to the following examples.

The following compounds 1 to 6 are used as examples to specifically describe the preparation method, the luminescent property and the application thereof in the organic electroluminescent diode device:

example 1: synthesis of Compound 1

Adding the compound 1-1(410mg,2.0mmol), iridium trichloride trihydrate (700mg,2.0mmol), ethylene glycol ethyl ether (150mL) and water (50mL) into a sealed tube, replacing the reaction atmosphere with nitrogen, heating the reaction solution to 100 ℃, stirring for 12 hours, cooling to room temperature, filtering out solids by suction and drying. Then, the resulting solid was put into a sealed tube, ligand L (270mg,0.63mmol), potassium tert-butoxide (280mg,2.5mmol) and anhydrous DMF (20mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e. compound 1(102mg, yield 10%). And (4) MS: 1628.53.

Example 2: synthesis of Compound 2

Compound 2-1(880mg,4.0mmol), iridium trichloride trihydrate (1.41g,4.0mmol), ethylene glycol ethyl ether (250mL) and water (80mL) were charged into a sealed tube, the reaction atmosphere was replaced with nitrogen, the reaction solution was heated to 100 ℃, stirred for 12 hours, cooled to room temperature, and the solid was filtered off with suction and dried. Then, the resulting solid was put into a sealed tube, ligand L (540mg,1.26mmol), potassium tert-butoxide (560mg,5.0mmol) and anhydrous DMF (40mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and then reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e., compound 2(168mg, yield 8%). 1696.55 for MS.

Example 3: synthesis of Compound 3

Compound 3-1(660mg,3.0mmol), iridium trichloride trihydrate (1.05g,3.0mmol), ethylene glycol ethyl ether (200mL) and water (70mL) were added to a sealed tube, the reaction atmosphere was replaced with nitrogen, the reaction solution was heated to 100 ℃, stirred for 12 hours, cooled to room temperature, and the solid was filtered off with suction and dried. Then, the resulting solid was put into a sealed tube, ligand L (400mg,0.94mmol), potassium tert-butoxide (420mg,3.7mmol) and anhydrous DMF (30mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e., compound 3(170mg, yield 11%). 1684.34 for MS.

Example 4: synthesis of Compound 4

Compound 4-1(567mg,2.0mmol), iridium trichloride trihydrate (700mg,2.0mmol), ethylene glycol ethyl ether (140mL) and water (40mL) were charged into a sealed tube, the reaction atmosphere was replaced with nitrogen, the reaction solution was heated to 100 ℃, stirred for 12 hours, cooled to room temperature, and the solid was filtered off with suction and dried. Then, the obtained solid was put into a sealed tube, ligand L (260mg,0.6mmol), potassium tert-butoxide (280mg,2.4mmol) and anhydrous DMF (20mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and then reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e. compound 4(96mg, yield 9%). And (4) MS:1941.42.

Example 5: synthesis of Compound 5

Adding the compound 5-1(298mg,1.0mmol), iridium trichloride trihydrate (350mg,1.0mmol), ethylene glycol ethyl ether (70mL) and water (20mL) into a sealed tube, replacing the reaction atmosphere with nitrogen, heating the reaction solution to 100 ℃, stirring for 12 hours, cooling to room temperature, filtering out solids by suction and drying. Then, the resulting solid was put into a sealed tube, ligand L (130mg,0.3mmol), potassium tert-butoxide (140mg,1.2mmol) and anhydrous DMF (10mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and then reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e. compound 5(55mg, yield 10%). And (4) MS:2001.55.

Example 6: synthesis of Compound 6

Adding the compound 6-1(300mg,1.0mmol), iridium trichloride trihydrate (350mg,1.0mmol), ethylene glycol ethyl ether (70mL) and water (20mL) into a sealed tube, replacing the reaction atmosphere with nitrogen, heating the reaction solution to 100 ℃, stirring for 12 hours, cooling to room temperature, filtering out solids by suction and drying. Then, the resulting solid was put into a sealed tube, ligand L (130mg,0.3mmol), potassium tert-butoxide (140mg,1.2mmol) and anhydrous DMF (10mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and then reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e. compound 6(70mg, yield 13%). And (4) MS: 1989.68.

Example 7: synthesis of Compound 7

Adding the compound 7-1(300mg,2.0mmol), iridium trichloride trihydrate (700mg,2.0mmol), ethylene glycol ethyl ether (140mL) and water (40mL) into a sealed tube, replacing the reaction atmosphere with nitrogen, heating the reaction solution to 100 ℃, stirring for 12 hours, cooling to room temperature, filtering out solids by suction and drying. Then, the obtained solid was put into a sealed tube, ligand L (260mg,0.6mmol), potassium tert-butoxide (280mg,2.4mmol) and anhydrous DMF (20mL) were added thereto, the atmosphere in the reaction flask was replaced with nitrogen, and the mixture was stirred at room temperature for 24 hours and then reacted at 100 ℃ for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, washing with water, filtering, purifying by column chromatography (petroleum ether: dichloromethane), and recrystallizing to obtain red iridium complex, i.e. compound 6(80mg, yield 7%). MS: MS: 1909.70.

Preparing a device:

the preparation of an OLED device comprising the above compound is described in detail below by means of specific examples. The structure of the OLED device is shown in FIG. 1, wherein 101 is a substrate; 102 is an anode; 103 is a hole injection layer; 104 is a hole transport layer; 105 is a light emitting layer; 106 is an electron transport layer; 107 is an electron injection layer; 108 is a cathode.

The device 1 is prepared as follows:

a. the ITO (indium tin oxide) conductive glass substrate is cleaned with various solvents (e.g., one or more of deionized water, chloroform, acetone, or isopropyl alcohol) for 15 minutes, and then subjected to ultraviolet ozone plasma treatment.

b. And moving the ITO conductive glass substrate into a vacuum vapor deposition device, and performing vacuum evaporation on Pt-301 under high vacuum to form a hole injection layer with the thickness of 10 nm.

c. An HTM material was deposited on the hole injection layer by high vacuum evaporation to form a hole transport layer (material: HT23) with a thickness of 10 nm.

d. Materials of a light-emitting layer (light-emitting host materials HT23 and ET24 in a weight ratio of 1: 1; light-emitting guest material compound 1, the doping amount of the guest material is 2% of the total mass of the host material) are evaporated on the hole transport layer in high vacuum to form the light-emitting layer with the thickness of 25 nm.

e. Compound ET24 was evaporated in high vacuum on the light-emitting layer to form a 24nm electron transport layer.

f. Electron injection layer: an electron injection layer having a thickness of 30nm was formed on the light-emitting layer by vacuum deposition of TmPyPB.

g. Cathode: and vacuum evaporating a cathode plated with metal LiF (1nm)/AI (100nm) on the electron injection layer.

h. Packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.

The device is prepared by vacuum evaporation in an environment of 1 × 10^-5Pa, the evaporation rate of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer is

The evaporation rate of the cathode layer is

The structures of the compounds involved in the OLED preparation are as follows:

device 2:

the same method as for the preparation of device 1, with the difference that: the guest material in the light-emitting layer is compound 2.

Device 3:

the same method as for the preparation of device 1, with the difference that: the guest material in the light-emitting layer is compound 3.

Device 4:

the same method of fabrication as device 1, except: the guest material in the light-emitting layer is selected from compound 4.

Device 5:

the same method as for the preparation of device 1, with the difference that: the guest material in the light-emitting layer is compound 5.

The device 6:

the same method as for the preparation of device 1, with the difference that: the guest material in the light-emitting layer is compound 6.

The device 7:

the same method of fabrication as device 1, except: the guest material in the light-emitting layer is selected from compound 7.

Comparative example device:

the same method of fabrication as device 1, except: the guest material in the light-emitting layer is REF-1, and the structural formula is as follows:

organic electroluminescent devices provided in examples 1 to 7 and comparative example were tested

In order to prove that the binuclear iridium complex of the pyrazole auxiliary ligand achieves the beneficial effects, the luminescent performance of the organic electroluminescent device prepared by the binuclear iridium complex is tested. The luminescence properties include luminescence efficiency, luminescence chromaticity, and device lifetime, wherein there are two commonly used methods for expressing luminescence efficiency: current efficiency and external quantum efficiency.

The current-voltage (J-V) characteristics of each OLED device were characterized by characterizing the device while recording LT95 lifetime and luminous efficiency, LT95@1000nits being the time for the luminance to drop from the initial luminance 1000nits to 95% of the initial luminance at constant current.

Peak data is from the EL (electroluminescence) spectrum of the IVL test.

Current Efficiency (CE), i.e. the ratio of the emitted light brightness to the corresponding current density.

External quantum efficiency (EQE, external quantum efficiency): the ratio of the number of photons emitted from the device to the number of carriers injected into the device.

Luminance chromaticity is a quantitative specification for the objective description and measurement of the color emitted by a device. The color of the spectrum emitted by the electrophosphorescent device was determined using a spectral radiometer according to the international commission on illumination (CIE) standard chromaticity system.

IVL tests were performed on each OLED device using Mc Science M6100 to obtain the results shown in the following table:

as can be seen from the table, the current efficiency and the external quantum efficiency of examples 1 to 7 are equivalent to those of the comparative example device, the wavelength of the device reaches over 640nm in the deep red region, the coordinate on the X axis of CIE is shifted by over 0.01, and the device enters the deep red region, so that the prior technical problem is solved. Furthermore, the lifetime of the device was improved by 78% for device 3 compared to the comparative example.

The organic compounds, mixtures, compositions and organic electronic devices provided in the examples of the present invention are described in detail, and the principles and embodiments of the present invention are described herein using specific examples, which are intended only to facilitate the understanding of the methods and their core concepts of the present invention; meanwhile, for those skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims

1. A binuclear iridium complex of a pyrazole auxiliary ligand is characterized in that: as shown in the general formula (I):

wherein, the first and the second end of the pipe are connected with each other,

R₁-R₁₁each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, a substituted or unsubstituted straight or branched alkyl group having 1 to 20C atoms, a substituted or unsubstituted branched alkyl or branched alkoxy group having 3 to 20C atoms, a substituted or unsubstituted cycloparaffin group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a combination of these groups;

the dotted line represents

A site of attachment to Ir.

2. The binuclear iridium complex as claimed in claim 1, wherein: r₁-R₁₁Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, a substituted or unsubstituted straight or branched alkyl group having 1 to 10C atoms, a substituted or unsubstituted branched alkyl or branched alkoxy group having 3 to 10C atoms, a substituted or unsubstituted cycloparaffin group having 3 to 10C atoms, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.

3. The dinuclear iridium complex of a pyrazole ancillary ligand according to claim 1, wherein: r is₁-R₁₁Independently at each occurrence is selected from H, D, a straight chain alkyl group having 1 to 10C atoms substituted with one or more D, a branched alkyl group having 3 to 10C atoms substituted with one or more D, or a group A:

wherein: r is₁₂Each occurrence is independently selected from H, D, cyano, nitro, CF₃Cl, Br, F, straight chain alkyl having 1 to 10C atoms substituted with one or more D, branched alkyl having 3 to 10C atoms substituted with one or more D, or phenyl;

denotes the attachment site.

4. The dinuclear iridium complex of a pyrazole ancillary ligand according to claim 1, wherein:

5. the dinuclear iridium complex of a pyrazole ancillary ligand according to claim 1, wherein: the binuclear iridium complex of the pyrazole auxiliary ligand is selected from the following structures:

6. a mixture, characterized by: the mixture comprises at least one binuclear iridium complex as an ancillary ligand of pyrazole as claimed in any of claims 1 to 5 and at least one organic functional material selected from hole-injecting materials, hole-transporting materials, electron-injecting materials, electron-blocking materials, hole-blocking materials, light-emitting guest materials, light-emitting host materials or organic dyes.

7. A composition characterized by: the composition comprises a dinuclear iridium complex of a pyrazole ancillary ligand according to any of claims 1 to 5 or a mixture according to claim 6, and at least one organic solvent.

8. An organic electronic device comprising at least one functional layer, characterized in that: the functional layer comprising a binuclear iridium complex as claimed in any one of claims 1 to 5 as an ancillary ligand for pyrazoles or a mixture as claimed in claim 6, or prepared from a composition as claimed in claim 7.

9. The organic electronic device of claim 8, wherein: the functional layer is selected from a light emitting layer.

10. The organic electronic device of claim 8, wherein: the organic electronic device is selected from an organic light-emitting diode, an organic photovoltaic cell, an organic light-emitting cell, an organic field effect tube, an organic laser, an organic spinning electronic device, an organic sensor and an organic plasmon emission diode.