CN114763341A

CN114763341A - Organic compound and application thereof in organic electronic device

Info

Publication number: CN114763341A
Application number: CN202210037938.5A
Authority: CN
Inventors: 文磊; 陈怀俊; 其他发明人请求不公开姓名
Original assignee: Zhejiang Brilliant Optoelectronic Technology Co Ltd
Current assignee: Zhejiang Brilliant Optoelectronic Technology Co Ltd
Priority date: 2021-01-13
Filing date: 2022-01-13
Publication date: 2022-07-19

Abstract

The invention discloses an organic compound and application thereof in an organic electronic device, in particular application in an organic electroluminescent diode. The invention also relates to organic electronic components, in particular organic electroluminescent diodes, containing the organic compounds according to the invention, to a method for the production thereof and to the use thereof in display and illumination technology. The compound has high thermal stability, and can improve the luminous efficiency and the service life of a device.

Description

Organic compound and application thereof in organic electronic device

Technical Field

The present invention relates to organic electronic materials and device technology, and in particular to organic compounds, mixtures comprising the same, compositions, and organic electronic devices thereof, particularly for use in organic electronic devices.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the versatility of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

Although a large number of OLED materials have been developed at present, there still exist many problems, and how to design a new material with better performance for adjustment, such as a high-performance electron transport material, so as to achieve the effects of reducing device voltage, improving device efficiency and prolonging device life is an urgent problem to be solved by those skilled in the art.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a class of organic compounds, mixtures and compositions comprising the same and their use in organic electronic devices, which aim to solve the problems of low efficiency and lifetime of existing organic electronic devices.

The technical scheme of the invention is as follows:

an organic compound having a structure represented by general formula (I):

wherein:

x is independently selected from N or CR₇And at least one X is N;

R₁-R₇at each occurrence, is independently selected from: hydrogen, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkoxy group having 1 to 20C atoms, or a straight-chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

l is selected from a single bond, or a substituted or unsubstituted aromatic group or heteroaromatic group with 6-30 ring atoms;

m and n are independently selected from 0 and 1, and m + n is more than or equal to 1;

o is selected from any integer from 0 to 4, and p is selected from any integer from 0 to 3.

A high polymer comprising at least one repeating unit comprising a structure corresponding to the organic compound described above.

A mixture comprising an organic compound or polymer as described above, and at least another organic functional material selected from one or more of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material, an organic dye.

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

An organic electronic device comprising a functional layer comprising or prepared from at least one organic compound or polymer or mixture as described above.

Has the advantages that: the organic compound can adjust the stacking among molecules due to the steric hindrance effect, is less prone to crystallization after film forming, and reduces the interaction among molecules, so that the effects of reducing exciton quenching and improving the energy utilization rate are achieved, and the efficiency and the service life of related materials and devices are improved.

Detailed Description

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

In the present invention, the composition and the printing ink, or ink, have the same meaning and may be interchanged.

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

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

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

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, an aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic ring systems or heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heteroaromatic groups are interrupted by short nonaromatic 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 aromatic groups for the purposes of this invention.

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

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, 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. 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, and the like.

The invention relates to an organic compound, which has a structure shown as a general formula (I):

wherein: x is independently selected from N or CR₇And at least one X is N; r₁-R₇At each occurrence, each is independently selected from: hydrogen, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkoxy group having 1 to 20C atoms, or a straight-chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; l is selected from a single bond, or a substituted or unsubstituted aromatic group or heteroaromatic group with 6-30 ring atoms; m and n are independently selected from 0 and 1, and m + n is more than or equal to 1;

In some preferred embodiments, R₁～R₇Each occurrence is independently selected from hydrogen, D, cyano, straight chain alkyl having 1 to 18C atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl having 3 to 18C atoms, or substituted or unsubstituted aromatic, heteroaromatic, aryloxy or heteroaryloxy having 5 to 30 ring atomsA group; in a more preferred embodiment, R₁～R₇Each occurrence is independently selected from D, a straight chain alkyl group having 1-12C atoms, or a substituted or unsubstituted aromatic, heteroaromatic, aryloxy or heteroaryloxy group having 5-20 ring atoms; in the most preferred embodiment, R₁～R₄Each occurrence is independently selected from D, a straight chain alkyl group having 1 to 6C atoms, or a substituted or unsubstituted aromatic, heteroaromatic, aryloxy, or heteroaryloxy group having 5 to 15 ring atoms.

In some preferred embodiments, R₁～R₇At each occurrence, it may be fully or partially deuterated, respectively.

In a preferred embodiment, the organic compound has a structure represented by one of general formulae (II-1) to (II-4):

wherein, X, R₁-R₆L, o, p, m, n have the meanings given above.

In a more preferred embodiment, the organic compound has a structure represented by general formulas (III-1) to (III-4):

wherein R is₁-R₆The meanings of L, o, p, m, n are as defined above.

In some preferred embodiments, L is selected from a single bond or the following groups:

wherein: x₂At each occurrence, is independently selected from CR₈Or N; y is₁At each occurrence, independently selected from NR₉、CR₁₀R₁₁、O、S、SiR₁₂R₁₃、S＝O、SO₂Or P (R)₁₄)；R₈-R₁₃At each occurrence, each is independently selected from: hydrogen, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkoxy group having 1 to 20C atoms, or a straight-chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

In some preferred embodiments, L, L₁And L₂Independently selected from the group comprising:

wherein: the H atoms on the ring may be further substituted.

In some preferred embodiments, L is selected from a single bond or the following groups and combinations:

wherein R is₁₅-R₄₂Has the same meaning as R₁。

L is selected from the group with the twisted structure, can effectively prevent molecule accumulation, improves the stability of the material and reduces the evaporation temperature, and simultaneously improves the transmission capability of the material due to the fact that the structure is guaranteed to have better conjugation.

In one embodiment, R₁-R₆Independently selected from the group consisting of:

wherein: x₁Selected from N or CR₁₀₁；Y¹Selected from O, S, S ═ O, SO₂、NR₁₀₂、CR₁₀₃R₁₀₄Or SiR₁₀₅R₁₀₆；R₁₀₁-R₁₀₆At each occurrence, is independently selected from: hydrogen, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkoxy group having 1 to 20C atoms, or a straight-chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

Further, R₁-R₆At each occurrence, is independently selected from the group consisting of:

these groups may optionally be substituted with 0,1,2 or 3 groups selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl and C3-C10 cycloalkyl. Wherein, A₁Selected from a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms.

In some embodiments, an organic compound according to the present invention is preferably selected from, but not limited to, the following structures:

in a preferred embodiment, the organic compounds according to the invention have a glass transition temperature 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 organic compounds according to the invention are partially deuterated, preferably 10% of the H are deuterated, more preferably 20% of the H are deuterated, preferably 30% of the H are deuterated, and most preferably 40% of the H are deuterated.

In a preferred embodiment, the organic compound according to the invention is a small molecule material.

In a preferred embodiment, the organic compounds according to the invention are used in evaporative OLED devices. For this purpose, the compounds according to the invention have a molecular weight of 1000g/mol or less, preferably 900g/mol or less, very preferably 850g/mol or less, more preferably 800g/mol or less, most preferably 700g/mol or less.

The invention also relates to a method for synthesizing organic compounds according to general formula (I), wherein starting materials containing reactive groups are used for the reaction. These active starting materials contain at least one leaving group, for example, bromine, iodine, boronic acid or boronic ester. Suitable reactions for forming C-C linkages are well known to those skilled in the art and described in the literature, and particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

The invention also relates to a high polymer, which comprises at least one repeating unit, wherein at least one repeating unit comprises a structure shown as the general formula (I). In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit of formula (I) is in a side chain. In another preferred embodiment, the polymer is a conjugated polymer. The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeat structure in small molecules. The small molecules have a molecular weight of less than or equal to 3000g/mol, preferably less than or equal to 2000g/mol, most preferably less than or equal to 1500 g/mol.

Polymers, i.e., polymers, include homopolymers (homo polymers), copolymers (copolymers), and block copolymers. In addition, in the present invention, the high polymer also includes Dendrimers (dendromers), and for the synthesis and use of Dendrimers, see [ Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle ].

Conjugated polymer (conjugated polymer) is a polymer whose backbone is mainly composed of sp2 hybridized orbitals of C atoms, notable examples being: polyacetylene and poly (phenylene vinylene) in which the C atoms of the main chain may also be replaced by other non-C atoms and still be considered as conjugated polymers when sp2 hybridization in the main chain is interrupted by some natural defect. In the present invention, the conjugated polymer may include arylamines (aryl amines), aryl phosphines (aryl phosphines) and other heterocyclic aromatic hydrocarbons (heterocyclic aromatics), organic metal complexes (organometallic complexes) in the main chain.

In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

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

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

In a preferred embodiment, the weight average molecular weight (Mw) of the polymer according to the present invention preferably ranges from 1 to 100 ten thousand, more preferably from 5 to 50 ten thousand, even more preferably from 10 to 40 ten thousand, even more preferably from 15 to 30 ten thousand, and most preferably from 20 to 25 ten thousand.

The invention also relates to a mixture comprising an organic compound as described above, and at least one further organic functional material selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), emitters (Emitter), Host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In a preferred embodiment, the mixture comprises an organic compound according to the invention and a phosphorescent emitter. The organic compounds according to the invention can be used as hosts, the phosphorescent emitters being present in an amount of up to 20% by weight, preferably up to 15% by weight, more preferably up to 10% by weight.

In a further preferred embodiment, the mixture comprises an organic compound according to the invention, a further host material and a phosphorescent emitter. The organic compounds according to the invention are used here as co-host materials in a proportion of > 10% by weight, preferably > 20% by weight, more preferably > 30% by weight, most preferably > 40% by weight.

In a preferred embodiment, the mixture comprises an organic compound according to the invention, a phosphorescent emitter and a host material. In such embodiments, the organic compounds according to the invention can be used as auxiliary luminescent materials in a weight ratio of from 1:2 to 2:1 with respect to the phosphorescent emitter. In a further preferred embodiment, the organic compounds according to the invention have a higher T1 than the phosphorescent emitters.

In certain embodiments, the mixture comprises an organic compound according to the present invention, and another TADF material.

In certain preferred embodiments, the mixture according to the invention comprises one organic functional material H1 selected from the group of organic compounds as described above, and at least one further organic functional material H2, H2 selected from the group of hole (also called hole) injecting or transporting materials (HIM/HTM), organic Host materials (Host).

In certain preferred embodiments, the organic mixtures according to the invention in which at least one of H1 and H2 has a value of ((LUMO +1) -LUMO) of 0.2eV or more, preferably 0.25eV or more, more preferably 0.3eV or more, still more preferably 0.35eV or more, very preferably 0.4eV or more, most preferably 0.45eV or more.

In a preferred embodiment, the organic mixtures according to the invention in which H1 has a value ((LUMO +1) -LUMO) of 0.2eV or more, preferably 0.25eV or more, more preferably 0.3eV or more, still more preferably 0.35eV or more, very preferably 0.4eV or more, most preferably 0.45eV or more.

In certain preferred embodiments, the organic mixtures according to the invention in which at least one of H1 and H2 ((HOMO- (HOMO-1)) > 0.2eV, preferably 0.25eV, more preferably 0.3eV, still more preferably 0.35eV, very preferably 0.4eV, most preferably 0.45eV are used.

In a preferred embodiment, the organic mixtures according to the invention in which H2 has a value ((HOMO- (HOMO-1)) > or more than 0.2eV, preferably > 0.25eV, more preferably > 0.3eV, more preferably > 0.35eV, very preferably > 0.4eV, most preferably > 0.45 eV.

In certain more preferred embodiments, the organic mixture 1) has a Δ E (S1-T1) of H1 of ≦ 0.30eV, preferably ≦ 0.25eV, more preferably ≦ 0.20eV, and most preferably ≦ 0.10eV, and/or 2) has a LUMO of H2 higher than that of H1 and a HOMO of H2 lower than that of H1.

In certain preferred embodiments, the organic mixture wherein H1 and H2 have a type II semiconductor heterojunction structure and min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)). ltoreq.min (ET (H1), ET (H2)) +0.1eV, wherein LUMO (H1), HOMO (H1) and ET (H1) are respectively the lowest unoccupied orbital, the highest occupied orbital, the energy level of triplet, LUMO (H2), HOMO (H2) and ET (H2) are respectively the lowest unoccupied orbital, the highest occupied orbital, the energy level of triplet, more preferred are ((LUMO (H1) -HOMO (H2), HOMO (H2) -HOMO (H2)). ltoreq.min (ET (H2), ET (H2)). ltoreq., ET (H2)) -0.1 eV.

In a preferred embodiment, the H1 and H2 have a type I semiconductor heterojunction structure, and the singlet level and triplet level differences (S1-T1) of H1 or H2 are less than or equal to 0.25eV, preferably less than or equal to 0.20eV, more preferably less than or equal to 0.15eV, and most preferably less than or equal to 0.10 eV.

In a preferred embodiment, the mixture wherein the molar ratio of H1 to H2 is from 1: 9 to 9: 1, preferably 2: 8 to 8: 2; preferred molar ratios are 3:7 to 7: 3; more preferred molar ratios are 4:6 to 6: 4; the most preferred molar ratio is 4.5:5.5 to 5.5: 4.5.

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

In another preferred embodiment, the mixture wherein the difference between the sublimation temperatures of H1 and H2 is no more than 50K; more preferably the difference in sublimation temperatures does not exceed 30K; more preferably, the difference in sublimation temperature does not exceed 20K; most preferably the difference in sublimation temperatures does not exceed 10K.

In a preferred embodiment, at least one of H1 and H2 in the mixture according to the invention has a Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 180 ℃ or higher.

The organic compounds according to the invention can be used as functional materials in functional layers of electronic devices. The functional layers include, but are not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).

In a preferred embodiment, the organic compounds according to the invention are used in the light-emitting layer.

In a preferred embodiment, the organic compounds according to the invention are used in electron transport layers.

Some details of phosphorescent emitters (triplet emitters), phosphorescent host materials (triplet host materials) and TADF emitters are described below (without being limited thereto).

1. Triplet Host material (Triplet Host):

examples of the triplet Host material are not particularly limited, and any metal complex or organic compound may be used as the Host as long as the triplet energy level thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter, and examples of the metal complex which can be used as the triplet Host (Host) include, but are not limited to, the following general structures:

m3 is a metal; (Y)₃-Y₄) Is a bidentate ligand, Y₃And Y₄Independently selected from C, N, O, P, and S; l is an ancillary ligand; r2 is an integer having a value from 1 to the maximum coordination number of the metal.

In a preferred embodiment, the metal complexes useful as triplet hosts are of the form:

(O-N) is a bidentate ligand in which the metal is coordinated to both the O and N atoms, and r2 is an integer having a value from 1 up to the maximum coordination number for the metal.

In certain embodiments, M3 may be selected from Ir and P.

Examples of the organic compound which can be a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine, and selenophene benzodipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.

In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

X₉is selected from CR¹R²Or NR¹；Y₂Selected from the group consisting of CR¹R²Or NR¹Or O or S; x¹–X⁸Each independently selected from CR⁸Or N and at least one is N, while R is in any two adjacent positions⁸An aliphatic or aromatic ring system which may be monocyclic or polycyclic; r¹-R⁸Has the same meaning as R₁And R is¹-R⁸Identical to or different from each other, R¹-R⁸Any one of which is the same or different in multiple occurrences. Ar (Ar)₁～Ar₃Each independently selected from 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 combinations thereof, wherein one or more Ar₁、Ar₂₁、Ar₃The radicals can form mono-or polycyclic, aliphatic or aromatic ring systems with one another and/or with the rings to which they are bonded.

Examples of suitable triplet host materials are listed below but are not limited to:

2. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7, 8-benzoquinoline derivative, a 2 (2-thienyl) pyridine derivative, a 2 (1-naphthyl) pyridine derivative, or a 2-phenylquinoline derivative. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

where M is a metal selected from the transition metals or the lanthanides or actinides, Ir, Pt, Au are particularly preferred.

Ar₄Each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)₅Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)₄And Ar₅Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0,1,2 or 3, preferably 2 or 3; q2 may be 0,1,2 or 3, preferably 1 or 0.

Examples of the extreme use of some triplet emitter materials can be found in the following patent documents and literature: WO, WO, WO, EP, EP 1191612, EP, WO, WO, US, WO, WO, WO, WO, WO, WO, WO, WO, WO, US A, US A, US A, Baldo, Thompson et al Nature 403, (2000), 750-Alphabet 753, US A, US A, Adachi et al.Appl.Phyt.Lett.78 (2001), 1622-Alphabet 1624, J.Kido et al.Appl.Phys.Lett.65(1994),2124, Kido et al chem.Lett.657,1990, US A, Johnson et al, JACS, Wright, JACS, Ma et al, Synth.metals, US, US, US, US A, WO A, WO A, WO A, CN A, WO A, WO 2013107487a1, WO 2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO 2014007565a1, WO 2014038456a1, WO 2014024131a1, WO 2014008982a1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed below:

TADF Material

The traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively utilized to emit light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials need to have a small difference in singlet-triplet energy levels, preferably Δ Est <0.3eV, less preferably Δ Est <0.2eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et al adv.adv.mater, 21,2009,4802, Adachi, et al.appl.phys.lett, 98,2011,083302, Adachi, et al.appl.phys.lett, 101,2012,093306, Adachi, et al.chem.commu., 48,2012,11392, Adachi, et al.nature Photonics,6,2012,253, Adachi, et al.nature,492,2012,234, Adachi, et al.j.chem.soc, am 23, Adachi, et al.adochi, et al.t.t.t.21, adochi.92, et al.nature, 358, Adachi et al.j.chechi.j.chem.soc.23, axm.7, adochi.92, ad.adachi.t.3892, et al.t.ad.t.t.t.ad.21, adachi.ad.ad.ad.ad.21, ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.r, ad.ad.21, ad.ad.ad.ad.ad.ad.ad.ad.i.t.t.t.r, ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.7, ad.ad.ad.ad.ad.ad.7, ad.ad.ad.ad.ad.ad.ad.ad.r.7, ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.ad.f. et.ad.7, ad.r, ad.ad.7, ad.7, ad.et.et.et.et.f. et.f. et.et al.f. et.f. et.et.ad.et.t.f. et.t.et.ad.t.t.7, ad.et.ad.f. publication, ad.7, ad.et al, ad.f. publication, ad.f. et al, ad.et al.f. et al.f. publication (a.et al, ad.f. et al, ad.f. et.et al, ad.et al, ad.ad.ad.f. publication, ad.ad.et al, ad.ad.ad.et al, ad.t.et al.ad.ad.ad.7, ad.et al, ad.t.t.t.t.t.t.f. publication (a.t.et al, ad.ad.et al, ad.t.et al, ad.t.t.t.ad.t.7, ad.et al, ad.ad.f. et al, ad.ad.ad.f. et al, ad.et al, ad.ad.f. et al, ad.f. publication (a.f. ad.f. publication (a.t.t.t.ad.ad.f. publication, ad.et.et.k.et.f. publication (a.t.f.et al, ad.k.7, ad.t.f. publication, ad.f.et al, ad.et al, ad.t.t.et al, ad.t.t.t.t.t.t.t.f.t.t.t.t.t.t.f.f.et.f.t.f.f.f.t.t.t.t.t.t.f.t.t.t.t.t.f.f.et al, ad.f.et.et.f.t.t.t.et al, ad.t.t.t.t.f.et.et.t.t.t.t.et.et.f.t.f. document.

Some examples of suitable TADF phosphors are listed below:

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, according to a composition of the invention, 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 solvents based on aromatic ethers 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, fenchytone, 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 present invention comprises 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:

delta d (dispersion force) is within the range of 17.0-23.2 MPa1/2, especially within the range of 18.5-21.0 MPa 1/2;

δ p (polar force) is in the range of 0.2-12.5 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2;

delta h (hydrogen bonding force) is in the range of 0.9-14.2 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2.

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions of the embodiments of the present invention may contain 0.01 to 10 wt%, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, and most preferably 0.25 to 3 wt% of the compound or mixture according to the present invention.

The invention also relates to the use of said composition as a coating or printing ink for producing organic electronic components, particularly preferably by printing or coating.

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, improving adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the Organic compound, polymer, mixture or composition as described above in an Organic electronic device, which may be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, photodiodes, Organic sensors, and Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), etc., and particularly preferably an OLED. In embodiments of the present invention, the compounds are preferably used in a hole transport layer of an OLED device.

The invention further relates to an organic electronic component comprising at least one functional layer comprising at least one organic compound, polymer, mixture or prepared from a composition as described above. Further, the organic electronic device comprises a cathode, an anode and at least one functional layer comprising a compound or mixture as described above or prepared from a composition as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL) and a Hole Blocking Layer (HBL); preferably, the functional layer is selected from hole transport layers.

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, photodiodes, Organic sensors, Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In 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 a preferred 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 of the p-type semiconductor material acting as 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 a preferred 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, 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 which 3 are 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

Reactant a (30.8g, 100.0mmol), pinacol diboron (38.1g, 150mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.7g, 5mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and then 500mL of 1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux reaction was maintained for 10 hours. After the reaction is finished, the reaction system is cooled to room temperature, the solvent in the reaction system is removed by rotary evaporation, dichloromethane and saturated sodium chloride solution are used for extraction, organic phases are combined, dried, filtered and concentrated, and then the product 1a is obtained, wherein the yield is about 29.8g, and the yield is 87%. Ms (asap) ═ 356.2.

Under a nitrogen atmosphere, intermediate 1a (29.0g, 81.4mmol), cyanuric chloride (7.5g, 40.7mmol), potassium carbonate (16.9g, 122.1mmol) and palladium tetratriphenylphosphine (2.3g, 2mmol) were added successively to a 1000mL three-necked flask, and then 400mL1, 4-dioxane and 50mL deionized water were injected successively into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 8 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: about 27g of product 1b was isolated by silica gel column chromatography with eluent of n-hexane 1:3 (volume ratio) at 74%. Ms (asap) ═ 571.2.

C (13.3g, 50mmol) was charged into a 500mL three-necked flask in a water-free and oxygen-free atmosphere, 200mL of anhydrous tetrahydrofuran was charged into the flask and stirred at-78 deg.C, and then an n-butyllithium-n-hexane solution (25mL, 75mmol) was slowly added dropwise to the reaction system and stirred at-78 deg.C for 2 hours. Next, the reaction mixture B (10g, 100mmol) was dissolved in 100mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, gradually warmed to room temperature, and stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, the solvent was removed, and the resulting product was dissolved with a concentrated hydrochloric acid/glacial acetic acid mixture (50mL/200mL) under nitrogen and refluxed at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is purified by dichloromethane: column chromatography purification with petroleum ether at 1:8 (by volume) as eluent gave about 12.1g of crude product 1c in about 86% yield. Ms (asap) ═ 280.1.

Intermediate 1c (12g, 42.8mmol), pinacol diboron diboride (13g, 51.4mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (1.6g, 2.1mmol) and potassium acetate (6.3g, 64.2mmol) were added sequentially to a 500mL three-necked flask under a nitrogen atmosphere, and then 300mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 9 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: the product 1d was about 11.8g after column chromatography with petroleum ether at 1:2 (vol/vol) as eluent, with a yield of 74%. Ms (asap) ═ 372.3.

Under a nitrogen atmosphere, intermediate 1b (21.3g, 37.3mmol), intermediate 1d (11.6g, 31.1mmol), potassium carbonate (6.4g, 46.7mmol), tetrakistriphenylphosphine palladium (1.8g, 1.6mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (1.5g, 3.2mmol) were sequentially charged into a 1000mL three-necked flask, and then 400mL1, 4-dioxane and 50mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding ethyl acetate: about 15g of the product (1) was obtained by silica gel column chromatography using n-hexane (1: 10 by volume) as an eluent, and the yield was 62%. Ms (asap) ═ 781.3.

Example 2

D (26.6g, 100mmol) was charged into a 1000mL three-necked flask in an anhydrous and oxygen-free environment, 300mL of anhydrous tetrahydrofuran was charged into the flask, and stirring was carried out at-78 ℃, then an n-butyllithium-n-hexane solution (50mL, 150mmol) was slowly added dropwise to the reaction system, and stirring was continued for 3 hours at-78 ℃. Then, the reaction mixture B (20g, 200mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, gradually warmed to room temperature, and further stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (50mL/200mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is extracted with dichloromethane: the crude product 2a was purified by column chromatography using 1:8 (by volume) eluent to give about 23g of crude product 2a in about 82% yield. Ms (asap) ═ 280.1.

Reactant E (46.3g, 100mmol), pinacol diboron diborate (30.5g, 120mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (2.9g, 4mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and 650mL1, 4-dioxane was then injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification of petroleum ether 1:2 (by volume) as eluent gave about 43.2g of product 2b in 84% yield. Ms (asap) ═ 511.2.

Under a nitrogen atmosphere, intermediate 2a (20g, 71.4mmol), intermediate 2b (40.1g, 78.5mmol), potassium carbonate (14.8g, 107.1mmol), tetrakistriphenylphosphine palladium (4.1g, 3.57mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (3.4g, 7.14mmol) were sequentially charged into a 1000mL three-necked flask, and then 500mL1, 4-dioxane and 100mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 18 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding ethyl acetate: about 32g of the product (2) was obtained by silica gel column chromatography with n-hexane 1:8 (volume ratio) as an eluent, with a yield of 71%. Ms (asap) ═ 628.3.

Example 3

Reactant F (30.1g, 100mmol), pinacol diboron diboride (30.5g, 120mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (2.9g, 4mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and then 500mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification of petroleum ether 1:3 (by volume) as eluent gave about 27.1g of product 3a in 76% yield. Ms (asap) ═ 358.1.

Under a nitrogen atmosphere, reactant G (24.3G, 62.8mmol), potassium carbonate (10.4G, 75.4mmol), tetrakistriphenylphosphine palladium (2.2G, 1.9mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (1.8G, 3.8mmol) were sequentially added to a 1000mL three-necked flask, 300mL1, 4-dioxane and 100mL deionized water were sequentially injected into the flask, then intermediate 3a (27G, 75.4mmol) was dissolved in 200mL1, 4-dioxane, slowly dropped into the reaction system and heated to reflux the solvent, and the reflux reaction was maintained for 12 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding ethyl acetate: about 23.4g of the product 3b was obtained by silica gel column chromatography with n-hexane (1: 10 by volume) as eluent, with a yield of 70%. Ms (asap) ═ 539.1.

Intermediate 3b (23g, 42.7mmol), pinacol diboron diborate (16.2g, 64mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (1.5g, 2.1mmol) and potassium acetate (6.3g, 64mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and 500mL1, 4-dioxane was then injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification with petroleum ether at 1:2 (by volume) as eluent gave about 16.6g of product 3c in 66% yield. Ms (asap) ═ 587.3.

Under a nitrogen atmosphere, intermediate 3c (16.5g, 28.1mmol), intermediate 2a (6.6g, 23.4mmol), potassium carbonate (4.8g, 35.1mmol), tetrakistriphenylphosphine palladium (1.4g, 1.2mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (1.1g, 2.4mmol) were sequentially charged into a 500mL three-necked flask, and then 200mL1, 4-dioxane and 40mL deionized water were sequentially injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux reaction was maintained for 10 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: about 11.4g of the product (3) was obtained by silica gel column chromatography with n-hexane (1: 5 by volume) as eluent, with a yield of 69%. Ms (asap) ═ 705.3.

Example 4

Reactant H (33.2g, 100mmol), potassium carbonate (20.7g, 150mmol) and palladium tetrakistriphenylphosphine (3.5g, 3mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and then 300mL1, 4-dioxane and 100mL deionized water were charged sequentially to the flask. Then, a solution of reactant I (25.5g, 110mmol) in 1, 4-dioxane was slowly added dropwise to the reaction system, and the solvent was refluxed by heating while maintaining the reflux for 18 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: the product 4a was isolated by silica gel column chromatography with n-hexane (1: 10 by volume) as eluent in a yield of about 29.4g (75%). Ms (asap) ═ 392.0.

Intermediate 4a (29.2g, 74.5mmol) was charged to a 1000mL three-necked flask in a water-free and oxygen-free environment, 300mL of anhydrous tetrahydrofuran was charged into the flask and stirred at-78 deg.C, then an n-butyllithium-n-hexane solution (37mL, 117mmol) was slowly added dropwise to the reaction system and stirring was continued at-78 deg.C for 3 hours. Then, the reaction mixture B (20g, 117mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, gradually warmed to room temperature, and further stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (75mL/300mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is purified by dichloromethane: column chromatography purification with petroleum ether at 1:5 (vol/vol) as eluent gave about 26g of crude 4b in about 86% yield. Ms (asap) ═ 406.2.

Reactant J (38.7g, 100mmol), pinacol diboron diborate (38.1g, 150mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.67g, 5mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and 600mL1, 4-dioxane was then injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 15 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification of petroleum ether in a volume ratio of 1:2 as eluent gave about 39.6g of product 4c in 91% yield. Ms (asap) ═ 435.2.

Under a nitrogen atmosphere, intermediate 4c (30g, 68.9mmol), intermediate 4b (25g, 57.4mmol), potassium carbonate (11.9g, 86.1mmol), tetrakistriphenylphosphine palladium (3.3g, 2.87mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (2.7g, 5.7mmol) were sequentially charged into a 1000mL three-necked flask, and then 500mL1, 4-dioxane and 100mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding dichloromethane: about 28.1g of the product (4) was obtained by silica gel column chromatography with n-hexane (1: 3 by volume) as eluent, with a yield of 72%. Ms (asap) ═ 679.3.

Example 5

Reactant K (23.2g, 100mmol), pinacol diboron diborate (38.1g, 150mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.67g, 5mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 500mL three-necked flask under a nitrogen atmosphere, and then 300mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 5 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification with petroleum ether at 1:4 (by volume) as eluent gave about 21.8g of product 5a in 94% yield. Ms (asap) ═ 232.

Reactant L (21.9g, 97.3mmol), intermediate 5a (21.5g, 92.7mmol), potassium carbonate (15.4g, 111.2mmol) and palladium tetratriphenylphosphine (3.2g, 2.78mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and 600mL of tetrahydrofuran and 150mL of deionized water were then sequentially charged to the flask. The reaction mixture was stirred at room temperature, then the solvent was refluxed by warming, and the reaction was maintained at reflux for 18 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding ethyl acetate: about 20.7g of product 5b was isolated by silica gel column chromatography with n-hexane 1:10 (volume ratio) as eluent, with a yield of 65%. Ms (asap) ═ 343.1.

A reactant M (26.7g, 100mmol) was charged into a 1000mL three-necked flask in an anhydrous and oxygen-free environment, then 300mL of anhydrous tetrahydrofuran was charged into the flask, and stirring was carried out at-78 ℃, then an n-butyllithium-n-hexane solution (40mL, 120mmol) was slowly added dropwise to the reaction system, and then stirring was continued at-78 ℃ for 3 hours. Then, reaction product B (20g, 120mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, then gradually warmed to room temperature, and stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (75mL/300mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is purified by dichloromethane: column chromatography purification with petroleum ether at 1:5 (vol/vol) as eluent gave about 20.1g of crude 5c in about 71.8% yield. Ms (asap) ═ 280.1.

Intermediate 5c (20g, 71.4mmol), pinacol diboron diborate (27.2g, 107mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.57g, 5mmol) and potassium acetate (10.5g, 107.1mmol) were added sequentially to a 500mL three-necked flask under a nitrogen atmosphere, and then 300mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: the product 5d is about 22.6g after column chromatography purification with eluent of 1:3 (volume ratio), and the yield is 85%. Ms (asap) ═ 372.2.

Under a nitrogen atmosphere, intermediate 5d (26g, 70mmol), intermediate 5b (20g, 58.3mmol), potassium carbonate (12.1g, 87.5mmol), palladium tetratriphenylphosphine (3.4g, 2.9mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (2.8g, 5.8mmol) were sequentially charged into a 500mL three-necked flask, and then 300mL1, 4-dioxane and 80mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 14 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: about 28.1g of the product (5) was obtained by silica gel column chromatography with n-hexane (1: 2 by volume) as an eluent in a yield of 72%. Ms (asap) ═ 553.3.

Example 6

A reactant N (26.7g, 100mmol) is added into a 1000mL three-neck flask under anhydrous and oxygen-free environment, then 300mL of anhydrous tetrahydrofuran is injected into the flask, stirring is carried out at-78 ℃, then an N-butyllithium-N-hexane solution (40mL, 120mmol) is slowly added dropwise into the reaction system, and then stirring is carried out for 3 hours at-78 ℃. Then, reaction product B (20g, 120mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, then gradually warmed to room temperature, and stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (75mL/300mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is purified by dichloromethane: the crude product 6a was obtained in about 21.3g and about 76% yield after column chromatography using 1:8 (by volume) petroleum ether as eluent. Ms (asap) ═ 280.1.

Reactant O (38.7g, 100mmol), pinacol diboron diborate (38.1g, 150mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.57g, 5mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and then 400mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 16 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: column chromatography purification of petroleum ether 1:3 (by volume) as eluent gave about 35.7g of product 6b in 82% yield. Ms (asap) ═ 435.2.

Under a nitrogen atmosphere, intermediate 6b (35.5g, 85.6mmol), intermediate 6a (20g, 71.3mmol), potassium carbonate (12.1g, 107mmol), tetrakistriphenylphosphine palladium (4.2g, 3.6mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (3.4g, 7.2mmol) were sequentially charged into a 1000mL three-necked flask, and then 600mL1, 4-dioxane and 100mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the solvent was refluxed by warming, and the reaction was maintained at reflux for 14 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding dichloromethane: about 31g of the product (6) was obtained by silica gel column chromatography with n-hexane (1: 2 by volume) as eluent in 78% yield. Ms (asap) ═ 553.3.

Example 7

A reactant P (26.7g, 100mmol) was charged into a 1000mL three-necked flask in an anhydrous and oxygen-free environment, then 300mL of anhydrous tetrahydrofuran was injected into the flask, and stirring was carried out at-78 ℃, then an n-butyllithium-n-hexane solution (40mL, 120mmol) was slowly added dropwise to the reaction system, and then stirring was continued at-78 ℃ for 3 hours. Then, reaction product B (20g, 120mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the solution was poured into the reaction system, stirred at-78 ℃ for 2 hours, then gradually warmed to room temperature, and stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (75mL/300mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is purified by dichloromethane: column chromatography purification with petroleum ether at 1:8 (by volume) as eluent gave about 22.7g of crude 7a in about 81% yield. Ms (asap) ═ 280.1.

Under a nitrogen atmosphere, intermediate 7a (22.5g, 80.3mmol), potassium carbonate (16.6g, 120.5 mmol) and tetratriphenylphosphine palladium (2.8g, 2.4mmol) were sequentially charged into a 500mL three-necked flask, then 200mL of toluene and 80mL of deionized water were sequentially charged into the flask, and then a toluene solution of reactant Q (19.3g, 96.4mmol) was slowly dropped into the reaction system. Then, the temperature was raised to reflux the solvent, and the reaction was maintained at reflux for 8 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding dichloromethane: about 26.7g of product 7b was isolated by silica gel column chromatography using n-hexane (1: 8 by volume) as eluent, with a yield of 83%. Ms (asap) ═ 400.1.

Reactant R (38.7g, 100mmol), pinacol diboron diborate (38.1g, 150mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.57g, 5mmol) and potassium acetate (14.7g, 150mmol) were added sequentially to a 1000mL three-necked flask under a nitrogen atmosphere, and 600mL1, 4-dioxane was then injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: the product 7c was obtained by column chromatography with 1:2 (by volume) petroleum ether as eluent in an amount of about 37.7g, with a yield of 87%. Ms (asap) ═ 435.2.

Under a nitrogen atmosphere, intermediate 7b (26.5g, 66.3mmol), intermediate 7c (34.6g, 79.6mmol), potassium carbonate (13.7g, 99.5mmol), tetrakistriphenylphosphine palladium (3.8g, 3.3mmol) and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (3.1g, 6.6mmol) were sequentially charged into a 1000mL three-necked flask, and then 500mL1, 4-dioxane and 100mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 14 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: about 31.3g of the product (7) was obtained by silica gel column chromatography using n-hexane (1: 4 by volume) as an eluent, with a yield of 75%. Ms (asap) ═ 629.3.

Example 8

Dissolving a reactant S (40g, 161.3mmol) in a 1000mL three-neck flask filled with 400mL dichloromethane under a nitrogen atmosphere, adding 50mL triethylamine, cooling to 0 ℃ in an ice-water bath, slowly dropwise adding 45mL trifluoromethanesulfonic anhydride into the reaction solution, pouring the reaction mixture into 1000mL deionized water after the reaction is completed, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and then adding dichloromethane: the product 8a was isolated by silica gel column chromatography with n-hexane 1:4 (vol) as eluent in about 55.2g with a yield of about 90%. Ms (asap) ═ 379.9.

Under a nitrogen atmosphere, intermediate 8a (50g, 131.6mmol), reactant T (29.4g, 131.6mmol), potassium carbonate (21.8g, 157.9), and palladium tetratriphenylphosphine (4.6g, 3.9mmol) were sequentially charged into a 1000mL three-necked flask, and then 500mL1, 4-dioxane, and 100mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate, combined with organic phases, dried, filtered and concentrated, and then treated by dichloromethane: about 35.6g of the product 8b was obtained by silica gel column chromatography using n-hexane (1: 10 by volume) as an eluent, and the yield was 79%. Ms (asap) ═ 342.

Intermediate 8b (35g, 102mmol) was charged into a 1000mL three-necked flask in an anhydrous and oxygen-free environment, 300mL of anhydrous tetrahydrofuran was charged into the flask, and stirring was carried out at-78 ℃, then an n-butyllithium-n-hexane solution (40.8mL, 122.4mmol) was slowly added dropwise to the reaction system, and stirring was continued for 3 hours at-78 ℃. Then, reactant B (13.5g, 122.4mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and the mixture was poured into the reaction system, and stirred at-78 ℃ for 2 hours, then gradually warmed to room temperature, and further stirred for 12 hours. Finally, deionized water was added to the reaction system to quench, remove the solvent, dissolve the resulting product with a concentrated hydrochloric acid/glacial acetic acid mixture (75mL/300mL) under nitrogen, and reflux was carried out at 110 ℃ for 8 hours. After the reaction is finished, liquid separation and drying are carried out, and the obtained crude product is treated by ethyl acetate: column chromatography purification with petroleum ether at 1:10 (by volume) as eluent gave about 30.1g of crude 8c in about 83% yield. Ms (asap) ═ 356.1.

Intermediate 8c (30g, 84.2mmol), pinacol diboron (32.1g, 126.3mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (3.1g, 4.2mmol) and potassium acetate (12.4g, 126.3mmol) were added sequentially to a 500mL three-necked flask under a nitrogen atmosphere, and then 300mL1, 4-dioxane was injected into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux reaction was maintained for 10 hours. And (3) cooling to room temperature after the reaction is finished, removing the solvent in the reaction system by rotary evaporation, and reacting the obtained crude product with dichloromethane: the product 8d is about 32.6g after column chromatography purification with eluent of 1:2 (volume ratio), and the yield is 91%. Ms (asap) ═ 434.2.

Under a nitrogen atmosphere, intermediate 8d (32g, 73.7mmol), reactant U (21.1g, 61.4mmol), potassium carbonate (12.7g, 92.1mmol), tetrakistriphenylphosphine palladium (4.3g, 3.7mmol), and 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (3.5g, 7.4mmol) were sequentially charged into a 1000mL three-necked flask, and then 600mL1, 4-dioxane and 150mL deionized water were sequentially charged into the flask. The reaction mixture was stirred at room temperature, then the temperature was raised to reflux the solvent, and the reflux was maintained for 12 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, combining organic phases, drying, filtering, concentrating, and adding dichloromethane: about 32.9g of the product (8) was obtained by silica gel column chromatography using n-hexane (1: 3 by volume) as an eluent, with a yield of 71%. Ms (asap) ═ 629.3.

2. Preparation and characterization of OLED device

The preparation of the OLED device using the above is described in detail by the following specific examples:

a. cleaning an ITO (indium tin oxide) conductive glass substrate: washing with various solvents (such as one or more of chloroform, acetone or isopropanol), and then performing ultraviolet ozone treatment.

b. Evaporation: moving the ITO substrate into a vacuum vapor deposition device under high vacuum (1X 10)^-6Mbar), a HI layer having a thickness of 30nm was formed using a resistance heating evaporation source, and 50nm of HT-1 was formed on the HI layer by heating in sequence, followed by evaporation of compound 1 on the HT-1 layer to form a 10nm HT-2 layer. Two evaporation sources were then used, the material was vaporized at different rates, and BH was packed: the BD has a weight ratio of 100:3, and a light-emitting layer of 25nm is formed. And then evaporating a first electron transport layer, putting ET and LiQ into different evaporation units, co-depositing the ET and the LiQ respectively according to the proportion of 50 wt% to obtain a second electron transport layer, then depositing LiQ with the thickness of 1nm as an electron injection layer, and finally depositing an Al cathode with the thickness of 100nm on the electron injection layer.

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

The structure of the device is HI (10)/HT-1(50)/HT-2 (10)/BH: BD 100:3 (25)/first ET transport layer (5)/second ET transport layer ET: LiQ 50:50(25)/LiQ (1)/Al (100)

HI (10)/HT-1(50)/HT-2 (10)/BH: BD 100:3 (25)/first ET transport layer (0)/second ET transport layer ET: LiQ 50:50(30)/LiQ (1)/Al (100)

The device performances of the above examples and comparative examples were tested and are specifically shown in table 1; wherein the driving voltage and current efficiency are 10mA/cm²Testing under current density; the device lifetime of T95 is 20mA/cm at constant current density²The luminance decayed to 95% of the time.

TABLE 1

Compared with the comparative example, the current efficiency and the service life of the devices in examples 1 to 8 are obviously improved, and the organic compound provided by the invention is applied to an electron transport material in an OLED device, so that the current efficiency and the service life of the device can be improved, and the driving voltage of the device can be reduced.

The embodiments described above only represent several embodiments of the present invention, and the description is 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 should be subject to the appended claims.

Claims

1. An organic compound having a structure represented by general formula (I):

wherein:

x is independently selected from N or CR₇And at least one X is N;

R₁-R₇at each occurrence, each is independently selected from: hydrogen, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkoxy group having 1 to 20C atoms, or a straight-chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, crosslinkableOr a substituted or unsubstituted aromatic group having from 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy group having from 5 to 60 ring atoms, or a heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;

m and n are each independently selected from 0,1, and m + n is greater than or equal to 1;

2. The organic compound of claim 1, wherein the organic compound is selected from the structures represented by general formulae (II-1) to (II-4):

wherein, X, R₁-R₆L, o, p, m, n have the meanings given in claim 1.

3. An organic compound according to claim 1 or 2, characterized in that L is selected from a single bond or the following groups and combinations thereof:

wherein:

X₂at each occurrence, is independently selected from CR₈Or N;

Y₁at each occurrence, independently selected from NR₉、CR₁₀R₁₁、O、S、SiR₁₂R₁₃、S＝O、SO₂Or P (R)₁₄)；

R₈-R₁₃At each occurrence, is independently selected from: hydrogen, D, or a straight chain alkyl group having 1 to 20C atomsAn alkoxy group, or a linear thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, 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, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF group, a formyl group, an isocyano group, an isocyanate, a thiocyanate₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

4. The organic compound according to any one of claims 1 to 3, wherein L is selected from a single bond or the group consisting of:

wherein R is₁₅-R₄₂Has the meaning of R in claim 1₁。

5. A polymer comprising at least one repeating unit comprising a structure corresponding to the organic compound according to any one of claims 1 to 4.

6. A mixture comprising an organic compound according to any one of claims 1 to 4 or a high polymer according to claim 5 and at least one further organic functional material selected from one or more of hole injecting materials, hole transporting materials, electron injecting materials, electron blocking materials, hole blocking materials, light emitting materials, host materials, organic dyes.

7. Composition comprising at least one organic compound according to any one of claims 1 to 4 or a polymer according to claim 5 or a mixture according to claim 6 and at least one organic solvent.

8. An organic electronic device comprising a functional layer, characterized in that the functional layer comprises at least one organic compound according to any of claims 1 to 4 or a high polymer according to claim 5 or a mixture according to claim 7.

9. The organic electronic device according to claim 8, wherein the organic electronic device is selected from the group consisting of organic light emitting diodes, organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spintronic devices, photodiodes, organic sensors, and organic plasmon emitting diodes.

10. The organic electronic device according to claim 9, wherein the organic electronic device is an organic electroluminescent device and comprises at least one organic compound according to any of claims 1 to 4 or a polymer according to claim 5 or a mixture according to claim 6.

11. The organic electronic device according to claim 10, wherein the functional layer is an electron transport layer.