CN114573587A

CN114573587A - Aromatic ring-fused cyclobutene organic compound, mixture, composition and organic electronic device

Info

Publication number: CN114573587A
Application number: CN202011385359.7A
Authority: CN
Inventors: 宋鑫龙; 何锐锋; 肖志华; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2020-12-01
Filing date: 2020-12-01
Publication date: 2022-06-03

Abstract

The invention discloses aromatic ring-fused cyclobutene organic compounds, mixtures, compositions and organic electronic devices. The structure of the aromatic ring-fused cyclobutene organic compound is shown as a general formula (I), and the aromatic ring-fused cyclobutene organic compound can be used as a doping material for a functional layer of an electronic device, so that the efficiency and the service life of the device are improved.

Description

Aromatic ring-fused cyclobutene organic compound, mixture, composition and organic electronic device

Technical Field

The invention relates to the field of organic electroluminescence, in particular to aromatic ring-fused cyclobutene organic compounds, mixtures, compositions and organic electronic devices.

Background

Organic Light Emitting Diodes (OLEDs) have the advantages of low cost, light weight, low operating voltage, high brightness, color tunability, wide viewing angle, easy assembly, and low power consumption in flat panel display and lighting applications, and thus are the most promising display technologies. In order to improve the light emitting efficiency of the organic light emitting diode, various fluorescent and phosphorescent based light emitting material systems have been developed. In order to improve the recombination efficiency of the injected holes and electrons, further improvement in the structure, material, and the like of the organic light emitting diode is required.

Currently, merck company utilizes aromatic diamine derivatives or aromatic fused ring diamine derivatives as hole transport materials of organic light emitting diodes to improve the efficiency of injecting holes, but the organic light emitting diodes can fully emit light only by increasing the use voltage, which leads to the problems of reduced service life and increased electricity consumption of the organic light emitting diodes.

The conventional method for reducing the use voltage is to dope an electron acceptor such as Tetracyanoquinodimethane (TCNQ), 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4TCNQ) in the hole transport layer of the organic light emitting diode. However, these compounds have a number of drawbacks when used for doping organic layers, such as: the operation is unstable in the manufacturing process of the organic light emitting diode, the stability is insufficient when the organic light emitting diode is driven, the life is reduced, or the above compound is diffused in the device to contaminate the device when the organic light emitting diode is manufactured by vacuum deposition.

Therefore, it is desired to further improve the electron acceptor doped in the hole transport layer to realize the low voltage and long lifetime of the organic light emitting diode.

Disclosure of Invention

Based on the above, there is a need to provide an aromatic ring-fused cyclobutene organic compound, which can be used as a doping material in a functional layer of an electronic device to improve the efficiency and lifetime of the device.

The invention is realized by the following technical scheme.

An aromatic ring-fused cyclobutene organic compound is characterized in that the structure of the compound is shown as the general formula (I):

wherein:

Ar¹、Ar²each independently selected from: substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms;

each occurrence of X is independently selected from CR₁、N、CR₁R₂、NR₁、SiR₁R₂、PR₁、O、S、SO₂Or C ═ M, and at least one X is selected from C ═ M;

m is independently selected from NR for each occurrence₃、CR₃R₄、PR₃、SiR₃R₄A substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;

R₁、R₂、R₃、R₄each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched-chain alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched-chain alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched-chain thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having from 6 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; two adjacent R₁With or without rings formed from each other.

The invention also provides a mixture which comprises at least one of the aromatic ring-fused cyclobutene organic compounds and at least one organic functional material, wherein the organic functional material can be selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting layer, a host material or an organic dye.

The invention also provides a composition which comprises at least one of the aromatic ring-fused cyclobutene organic compounds and the mixture and at least one organic solvent.

The invention also provides an organic electronic device which comprises at least one of the aromatic ring-fused cyclobutene organic compounds and the mixtures or is prepared from the composition.

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

the aromatic ring cyclobutene organic compound has excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can also be used as a dopant doped in the hole injection layer or the hole transport layer, so that the aromatic ring cyclobutene organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged.

Drawings

Fig. 1 is a schematic structural diagram of an organic light emitting device according to an embodiment of the present invention;

in the drawing, 101 denotes a substrate, 102 denotes an anode, 103 denotes a Hole Injection Layer (HIL), 104 denotes a Hole Transport Layer (HTL), 105 denotes a light-emitting layer, 106 denotes an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 107 denotes a cathode.

Detailed Description

The aromatic ring-fused cyclobutene organic compounds, mixtures, compositions and organic electronic devices of the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In the present invention, the composition and the printing ink or ink have the same meaning and are interchangeable with each other.

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

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

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substitutedIs substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c_1-30Alkyl, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may be further substituted with art-acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to H, C_1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c_1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

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

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

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

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

in the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site;

in the present invention, when a fused site is not specified in a group, it means that an optionally fused site in the group is a fused site, and preferably two or more sites in the ortho-position in the group are fused sites;

in the present invention, the substituent is linked to a mono-groupThe bond extending through the respective ring, meaning that the substituent may be attached to the ring at an optional position, e.g.

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

An aromatic ring-fused cyclobutene organic compound is characterized in that the structure is shown as the general formula (I):

wherein:

R₁、R₂、R₃、R₄each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxy having 7 to 20C atomsAlkylcarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having from 6 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; two adjacent R₁With or without rings formed from each other.

In one embodiment, Ar¹、Ar²Each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic group having 6 ring atoms; in one specific example, Ar¹、Ar²Are each independently selected from

Wherein: y is selected from CR₅N, P or SiR₅；

R₅Each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched-chain alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched-chain alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched-chain thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF₃、OCF₃Cl, Br, F, substituted or unsubstituted aromatic radicals having from 6 to 40 ring atoms, substituted or unsubstituted heteroaromatic radicals having from 5 to 40 ring atoms, substituted or unsubstituted aryloxy radicals having from 6 to 40 ring atomsA heteroaryloxy group of 5 to 40 ring atoms, or a combination of these systems.

In one specific example, Ar¹、Ar²Each independently selected from the group consisting of:

wherein denotes a fused site.

Further, Ar¹And Ar²Selected from the same group.

In one specific example, the structure of the aromatic ring-fused cyclobutene organic compound is shown as general formula (II-1) or (II-2):

in one specific example, the structure of the aromatic ring-fused cyclobutene organic compound is shown as the general formula (III-1):

each occurrence of X is independently selected from CR₁、N、CR₁R₂、NR₁、SiR₁R₂、PR₁、O、S、SO₂。

In a specific example, the structure of the aromatic ring-fused cyclobutene organic compound is selected from the structures represented by any one of general formulas (III-2), (III-3) and (III-4):

In one specific example, the structure of the aromatic ring-fused cyclobutene organic compound is shown as the general formula (III-5):

In one specific example, the structure of the aromatic ring-fused cyclobutene organic compound is shown as the general formula (III-6):

each occurrence of X is independently selected from CR₁Or N.

In one particular example of this, the first and second,

selected from any of the following structures:

wherein each occurrence of E is independently selected from CR₇R₈、NR₇O, S or SO₂；

R₆、R₇、R₈Each occurrence is independently selected from: H. d, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, a silyl group, a substituted ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a halomethyl groupAcyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, nitroso, CF₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 carbon atoms, an aryloxy or heteroaryloxy group having 5 to 40 carbon atoms, or a combination thereof.

In one particular example of this, the first and second,

selected from G1, G2, or G4;

wherein R is₃、R₄、R₇、R₈Each occurrence is independently selected from: D. cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, nitro, CF₃、OCF₃Cl, Br, F, by at least one R₂₀Substituted aromatic radicals having 6 to 10 ring atoms, substituted by at least one R₂₀A substituted heteroaromatic group having 5 to 10 ring atoms;

R₂₀each occurrence is independently selected from: cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, nitro, CF₃、OCF₃Cl, Br or F.

In one specific example, G1 is selected from any one of the following groups:

in one specific example, the structure of the aromatic ring-fused cyclobutene organic compound is selected from the structures represented by any one of the general formulae (III-2), (III-3), (III-4) and (III-6), and

selected from G1 or G4; wherein E is independently selected from CR₇R₈；R₃、R₄、R₇、R₈At each occurrence, is independently selected from cyano or nitro.

In one of themIn one specific example, two adjacent R₁Can be connected to each other to form a ring system; further, two adjacent R₁May be bonded to each other to form a substituted or unsubstituted aromatic ring system having 6 to 10 ring atoms, a heteroaromatic ring system having 5 to 10 ring atoms, or a cycloalkyl group or an alicyclic group having 3 to 10 ring atoms.

Preferably, the structure of the aromatic ring-fused cyclobutene organic compound is selected from the general formula (III-2) or (III-6); more preferably, it is selected from (III-6).

In one specific example, two adjacent R₁Can be mutually connected to form a ring system, and the structure of the aromatic ring-fused cyclobutene organic compound is shown as a general formula (IV-1) or (IV-2):

wherein Ar is³、Ar⁴Each independently selected from: a substituted or unsubstituted aromatic ring system having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic ring system having 5 to 10 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 10 ring atoms.

In one specific example, Ar³、Ar⁴Each independently selected from the group consisting of:

wherein:

denotes the fusion site;

X₁each occurrence is independently selected from CR₉Or N;

Y₁at each occurrence, independently selected from NR₁₀、CR₁₀R₁₁、SiR₁₀R₁₁、O、S、S(＝O)₂Or S (═ O);

R₉、R₁₀、R₁₁each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkane having 1 to 20C atomsOxy, thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having 5 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having 5 to 40 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; two adjacent R₉Form a ring or not form a ring; r₁₀、R₁₁With or without rings formed from each other.

specific examples of the compounds according to the invention are given below by way of illustration and not of limitation:

the aromatic ring-fused cyclobutene organic compound can be used as a functional material for electronic devices. Organic functional materials 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 particularly preferred embodiment, the aromatic-cyclo-butene-based organic compounds according to the present invention are used in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).

In a very preferred example, the aromatic cyclo-butene organic compounds according to the present invention are used as p-type doping materials in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).

In certain examples, the aromatic ring-fused cyclobutene organic compound according to the invention, T thereof₁More preferably, it is not less than 0.3eV, still more preferably not less than 0.6eV, particularly preferably not less than 0.8 eV.

Good thermal stability is required as a functional material. In general, the aromatic ring-fused butene organic compounds according to the present 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.

An appropriate LUMO level is necessary as a p-type dopant material. In some embodiments, the aromatic ring-fused cyclobutene organic compounds according to the invention have a LUMO ≦ -5.30eV, more preferably ≦ -5.50eV, and most preferably ≦ -5.60 eV.

In certain preferred embodiments, the aromatic-ring-butene-based organic compound according to the present invention ((HOMO- (HOMO-1)) is greater than or equal to 0.2eV, preferably greater than or equal to 0.25eV, more preferably greater than or equal to 0.3eV, more preferably greater than or equal to 0.35eV, even more preferably greater than or equal to 0.4eV, and most preferably greater than or equal to 0.45 eV.

The invention also provides a mixture, which comprises the aromatic ring-cyclobutene organic compound and at least one of the polymers, and at least one organic functional material, wherein the at least one organic functional material can be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a Host material (Host) or an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In some preferred examples, the mixture, wherein the another organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), or a Host material (Host).

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.2eV of another organic functional material.

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.1eV of another organic functional material.

In certain particularly preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO of another organic functional material.

In one example, the mixture according to the invention comprises at least one Hole Injection Material (HIM) or hole transport material and a dopant, which is an aromatic ring-benzocyclobutene organic compound as described above, in a molar ratio of dopant to host of from 1:1 to 1: 100000.

Details of HIM/HTM/EBM, and Host (Host material/matrix material) are described in WO2018095395A 1.

It is another object of the present invention to provide a material solution for printing OLEDs.

In some examples, the aromatic ring-fused cyclobutene organic compound according to the invention has a molecular weight of 800g/mol or more; preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.

In other examples, the aromatic ring-fused cyclobutene organic compounds according to the present invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, and most preferably 5mg/ml or more at 25 ℃.

The invention also provides a composition comprising at least one of the aromatic ring-fused cyclobutene organic compounds or mixtures as described above, and at least one organic solvent selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, borate or phosphate compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that the 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 their derivatives such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.

In some preferred examples, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred examples, 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 examples, the at least one organic solvent is selected from: 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 examples, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters in the following ranges:

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

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

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

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

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

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

The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like.

The compositions of the present invention may comprise from 0.01 to 20% by weight of an aromatic ring-fused cyclobutene organic compound or mixture according to the present invention, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 5% by weight, most preferably from 0.25 to 3% by weight.

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

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset 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 present invention also provides the use of an aromatic ring-fused cyclobutene organic compound, mixture or composition as described above in an organic electronic device selected from, but not limited to: organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronics, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., with OLEDs being particularly preferred. In the present examples, the organic compound or mixture or composition is preferably used in a hole transport layer or a hole injection layer of an OLED device.

The invention also provides an organic electronic device which comprises at least one of the aromatic ring-butene organic compounds or the mixture or is prepared from the composition. Furthermore, the organic electronic device at least comprises a functional layer, wherein the functional layer comprises an aromatic ring-butene organic compound or a mixture thereof; 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), or a Hole Blocking Layer (HBL).

In a preferred embodiment, the organic electronic device according to the present invention comprises at least one hole injection layer or hole transport layer, and the hole injection layer or hole transport layer comprises an aromatic ring-fused cyclobutene organic compound as described above.

In the above-mentioned light emitting device, in particular an OLED, 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. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer, or glass. The substrate preferably has a smooth surface. Substrates free of surface defects are 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 polyethylene 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 the Hole Injection Layer (HIL), the Hole Transport Layer (HTL), or the light emitting 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 physical vapor deposition methods 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 example, 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 for OLEDs are possible as cathode materials for the devices according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL).

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 and 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 organic compounds

Example 1: synthesis of Compound DPI-1

Synthesis of compound a 1:

the compound 4, 7-dibromo-2, 1, 3-benzothiadiazole (2.91g, 10mmol), sodium borohydride (NaBH4, 1.54g, 40mmol), acetonitrile 40ml were stirred at 30-40 degrees overnight, the reaction product was cooled to room temperature, and 200ml of distilled water was added, then the formed precipitate was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to prepare the desired solid compound a1(1.39g, 53%), MS: [ M + H ] + ] 264.

Synthesis of compound a 2:

compound a1(5.28g, 20mmol), squaric acid (1.13g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give a2(3.62g, 64%), MS: [ M + H ] + ═ 568.

Synthesis of Compound DPI-1:

sodium tert-butoxide (4.86g, 50mmol) and A3(2.64g, 40mmol) were stirred under nitrogen, dry tetrahydrofuran for 15min, and A2(5.67g, 10mmol), Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol) and cuprous iodide (7.8g, 40mmol) were stirred at 60 ℃ for 12 hours, and then diluted with waterQuenching with cold concentrated hydrochloric acid, concentrating with dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 deg.C, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching with distilled water, continuing stirring after the solid is precipitated, and obtaining orange solid, DPI-1(4.12g, 81%), MS: [ M + H ], (M + H)]⁺＝509。

Example 2: synthesis of Compound DPI-2

Synthesis of Compound DPI-2:

sodium tert-butoxide (4.86g, 50mmol) and A5(6.08g, 40mmol) were stirred under nitrogen, dry tetrahydrofuran for 15min, and A2(5.67g, 10mmol), Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, DPI-2(3.58g, 42%), MS: [ M + H ], [ M ] and (B ], [ M ], [ 10 ], [ M ], [ 0 ], [ 1 ], [ M ] and [ n ] and [ n ] are obtained in each of]⁺＝853。

Example 3: synthesis of Compound DPI-3

Synthesis of Compound DPI-3:

sodium tert-butoxide (4.86g, 50mmol) and A7(2.08g, 40mmol) were stirred under nitrogen, dry tetrahydrofuran for 15min, and A2(5.67g, 10mmol), Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol) and cuprous iodide (7.8g, 40mmol) were stirred at 60 deg.CStirring for 12H, quenching with cold concentrated hydrochloric acid, concentrating with dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 deg.C, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching with distilled water, continuing stirring after the solid is precipitated, and obtaining DPI-3(3.39g, 75%) as an orange solid]⁺＝452。

Example 4: synthesis of Compound DPI-4

Synthesis of Compound DPI-4:

sodium tert-butoxide (4.86g, 50mmol) and A9(3.44g, 40mmol) were stirred under nitrogen, dry tetrahydrofuran for 15min, and A2(5.67g, 10mmol), Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid is precipitated, obtaining an orange solid, obtaining DPI-4(1.12g, 19%), MS: [ M + H ], [ M + H ]]⁺＝589。

Example 5: synthesis of Compound DPI-5

Synthesis of compound a 12:

compound A10(10mmol), A11(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A12(3.21mmol, 32.1%), MS: [ M + H ]]⁺＝408。

Synthesis of Compound DPI-5:

sodium tert-butoxide (50mmol) and A13(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A12(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-5(2.83mmol, 28.3%), MS: [ M + H ], [ M + H ]]⁺＝677。

Example 6: synthesis of Compound DPI-6

Synthesis of compound a 16:

compound A14(10mmol), A15(10mmol), squaric acid (10mmol),100ml concentrated sulfuric acid and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A16(6.43mmol, 64.3%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝805。

Synthesis of Compound DPI-6:

sodium tert-butoxide (50mmol) and A17(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A16(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is complete, quenching the reaction with distilled water, precipitating a solid, and removing the solidStirring was continued after which an orange solid was obtained, giving DPI-6(5.33mmol, 53.3%), MS: [ M + H ]]⁺＝877。

Example 7: synthesis of Compound DPI-7

Synthesis of compound a 20:

compound A18(10mmol), A19(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A20(3.16mmol, 31.6%), MS: [ M + H ]]⁺＝455。

Synthesis of Compound DPI-7:

sodium tert-butoxide (50mmol) and A17(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A20(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid is precipitated, obtaining an orange solid, obtaining DPI-7(3.74mmol, 37.4%), MS: [ M + H ]]⁺＝528。

Example 8: synthesis of Compound DPI-8

Synthesis of compound a 21:

compound A1(10mmol), A19(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A21(4.34mmol, 43.4%), MS: [ M + H ]]⁺＝413。

Synthesis of Compound DPI-8:

sodium tert-butoxide (50mmol) and A3(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A21(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid is precipitated, obtaining an orange solid, obtaining DPI-8(2.93mmol, 29.3%), MS: [ M + H ], [ M + H ]]⁺＝384。

Example 9: synthesis of Compound DPI-9

Synthesis of compound a 22:

compound A1(10mmol), A11(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A22(5.73mmol, 57.3%), MS: [ M + H ]]⁺＝461。

Synthesis of Compound DPI-9:

sodium tert-butoxide (50mmol) and A23(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A22(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol) followed by stirring at 60 ℃ for 12 hours, then quenching with cold concentrated hydrochloric acid, dichloromethane concentration, then drying over anhydrous sodium sulfate, distillation under reduced pressure, recrystallization of the residue with DCM/MeOH, dissolution of the product after recrystallization with glacial acetic acid, then cooling to 0 ℃, then addition of a mixture of nitric acid and hydrobromic acid, stirring at room temperature after addition is complete, quenching with distilled water, precipitation of a solid followed by continued stirring to give an orange solidTo obtain DPI-9(4.39mmol, 43.9%), MS: [ M + H ]]⁺＝384。

Example 10: synthesis of Compound DPI-10

Synthesis of compound a 25:

compound A24(20mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A25(6.31mmol, 63.1%) MS: [ M + H ]]⁺＝411。

Synthesis of Compound DPI-10:

sodium tert-butoxide (50mmol) and A26(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A25(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid is precipitated, obtaining an orange solid, obtaining DPI-10(6.93mmol, 69.3%), MS: [ M + H ], []⁺＝666。

Example 11: synthesis of Compound DPI-11

Synthesis of compound a 28:

compound A27(20mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A28(3.97mmol, 39.7%) MS: [ M + H ]]⁺＝563。

Synthesis of Compound DPI-11:

sodium tert-butoxide (50mmol) and A3(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A28(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol) followed by stirring at 60 degrees for 12 hours, followed by quenching with cold concentrated hydrochloric acid, concentration of dichloromethane, followed by drying over anhydrous sodium sulfate, distillation under reduced pressure, recrystallization of the residue with DCM/MeOH, dissolution of the recrystallized product with glacial acetic acid, followed by cooling to 0 degrees, addition of a mixture of nitric acid and hydrobromic acid, stirring at room temperature after addition was complete, quenching with distilled water, precipitation of a solid followed by continued stirring to give an orange solid, followed by DPI-11(5.11mmol, 51.1%), MS: [ M + H ], [ M + H ]]⁺＝536。

Example 12: synthesis of Compound DPI-12

Synthesis of compound a 30:

compound A29(20mmol), squaric acid (10mmol),100ml concentrated sulfuric acid and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and washed with ethanol and water to give A30(2.77mmol, 27.7%), MS: [ M + H ]]⁺＝515。

Synthesis of Compound DPI-12:

sodium tert-butoxide (50mmol) and A7(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A30(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying with anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid is precipitated, obtaining an orange solid, obtaining DPI-12(4.63mmol, 46.3%), MS: [ M + H ], [ M + H ]]⁺＝460。

Example 13: synthesis of Compound DPI-13

Synthesis of compound a 33:

compound A31(10mmol), A32(10mmol), squaric acid (10mmol),100ml concentrated sulfuric acid and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A33(7.31mmol, 73.1%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝558。

Synthesis of Compound DPI-13:

sodium tert-butoxide (50mmol) and A3(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A33(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-13(5.26mmol, 52.6%), MS: [ M + H ], [ M + H ]]⁺＝530。

Example 14: synthesis of Compound DPI-14

Synthesis of compound a 35:

compound A1(10mmol), A34(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A35(5.68mmol, 56.8%), MS: [ M + H ]]⁺＝557。

Synthesis of Compound DPI-14:

sodium tert-butoxide (50mmol) and A36(60mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A35(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-14(7.36mmol, 73.6%), MS: [ M + H ], [ M + H ]]⁺＝622。

Example 15: synthesis of Compound DPI-15

Synthesis of compound a 38:

compound A10(10mmol), A37(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A38(6.72mmol, 67.2%), MS: [ M + H ]]⁺＝508。

Synthesis of Compound DPI-15:

sodium tert-butoxide (50mmol) and A3(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A38(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-15(8.11mmol, 81.1%), MS: [ M + H ]]⁺＝495。

Example 16: synthesis of Compound DPI-16

Synthesis of compound a 41:

compound A39(10mmol), A40(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A41(6.16mmol, 61.6%), MS: [ M + H ]]⁺＝496。

Synthesis of Compound DPI-16:

sodium tert-butoxide (50mmol) and A7(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A41(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-16(7.53mmol, 75.3%), MS: [ M + H ]]⁺＝468。

Example 17: synthesis of Compound DPI-17

Synthesis of compound a 44:

compound A42(10mmol), A43(10mmol), squaric acid (10mmol),100ml concentrated sulfuric acid and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A44(5.42mmol, 54.2%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝557。

Synthesis of Compound DPI-17:

sodium tert-butoxide (50mmol) and A3(40mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A44(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol) followed by stirring at 60 degrees for 12 hours, followed by quenching with cold concentrated hydrochloric acid, concentration of dichloromethane, followed by drying over anhydrous sodium sulfate, distillation under reduced pressure, recrystallization of the residue with DCM/MeOH, dissolution of the recrystallized product with glacial acetic acid, followed by cooling to 0 degrees, addition of a mixture of nitric acid and hydrobromic acid, stirring at room temperature after addition was complete, quenching with distilled water, precipitation of a solid followed by continued stirring to give an orange solid, followed by DPI-17(6.58mmol, 65.8%) MS: [ M + H ], [ M + H ]]⁺＝528。

Example 18: synthesis of Compound DPI-18

Synthesis of compound a 46:

compound A45(20mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A46(6.28mmol, 62.8%), MS: [ M + H ]]⁺＝667。

Synthesis of Compound DPI-18:

sodium tert-butoxide (50mmol) and A3(80mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A46(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-18(5.61mmol, 56.1%), MS: [ M + H ]]⁺＝608。

Example 19: synthesis of Compound DPI-19

Synthesis of compound a 49:

compound A47(10mmol), A48(10mmol), squaric acid (10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered and washed with ethanol and water to give A49(7.11mmol, 71.1%), MS: [ M + H ]]⁺＝497。

Synthesis of Compound DPI-19:

sodium tert-butoxide (50mmol) and A3(20mmol) were stirred under nitrogen and dry tetrahydrofuran for 15min, and A49(10mmol) and Pd (PPh) were added at room temperature₃)₄(6.8g, 6mmol), cuprous iodide (7.8g, 40mmol), stirring at 60 ℃ for 12 hours, quenching with cold concentrated hydrochloric acid, concentrating dichloromethane, drying over anhydrous sodium sulfate, distilling under reduced pressure, recrystallizing the residue with DCM/MeOH, dissolving the recrystallized product with glacial acetic acid, cooling to 0 ℃, adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after the addition is completed, quenching the reaction with distilled water, continuing stirring after the solid precipitates, obtaining an orange solid, obtaining DPI-19(4.84mmol, 48.4%), MS: [ M + H ]]⁺＝483。

2. Energy level calculation of Compounds

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, S1, T1 and resonance factor f (S1) were used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO, LUMO, T1 and S1 are direct calculations of Gaussian09W in Hartree. The results are shown in the following table:

material	HOMO[eV]	LUMO[eV]	T1[eV]	S1[eV]
					Compound DPI-1	-7.34	-5.32	0.97	2.01
Compound DPI-2	-7.10	-5.27	0.87	1.93
					Compound DPI-3	-7.39	-5.04	0.79	1.81
Compound DPI-4	-7.23	-5.29	0.93	1.96
					Compound DPI-5	-7.14	-5.11	0.81	2.01
Compound DPI-6	-7.26	-5.08	0.94	2.10
					Compound DPI-7	-7.16	-5.19	0.79	1.94
Compound DPI-8	-7.14	-5.51	0.99	1.93
					Compound DPI-9	-7.32	-5.21	1.01	1.94
Chemical combinationDPI-10 for articles	-7.21	-5.10	0.89	1.86
					Compound DPI-11	-7.17	-5.14	0.92	2.10
Compound DPI-12	-7.21	-5.12	0.93	1.94
					Compound DPI-13	-7.34	-5.31	1.07	1.98
Compound DPI-14	-7.25	-5.19	0.94	1.87
					Compound DPI-15	-7.41	-5.37	0.97	1.88
Compound DPI-16	-7.12	-5.24	0.98	2.01
					Compound DPI-17	-7.16	-5.08	1.02	2.07
Compound DPI-18	-7.31	-5.42	0.87	2.10
					Compound DPI-19	-7.18	-5.16	0.94	2.06
Comparative Compound 1(F4TCNQ)	-7.84	-5.30	0.48	2.59

Preparation and characterization of OLED devices:

materials used for the layers of the OLED device:

the organic light-emitting device structure is shown in fig. 1, and the device structure is as follows: ITO/HI (10nm)/HT-1(120nm)/HT-2(10nm)/BH: BD (25nm)/ET: Liq30nm)/Liq (1nm)/Al (100nm), and the preparation method comprises the following specific steps:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. HI (10nm), HT-1(120nm), HT-2(10nm), EML (20nm), ETL (30 nm): the ITO substrate was transferred into a vacuum vapor deposition apparatus and evaporated under high vacuum (1X 10-6 mbar) using resistive heating, HT-1 and DPI-1 were heated at a rate of 98: 2 to form a10 nm implanted layer, followed by sequential evaporation to form 120nm HT-1 and 10nm HT-2 layers. Then BH and BD were measured at 97: 3 to form a25 nm light-emitting layer. Then, placing ET and LiQ in different evaporation units, carrying out co-deposition on the ET and the LiQ respectively according to the proportion of 50 weight percent, forming an electron transport layer with the thickness of 30nm on the luminescent layer, then depositing LiQ with the thickness of 1nm on the electron transport layer to be used as an electron injection layer, and finally depositing an Al cathode with the thickness of 100nm on the electron injection layer;

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

All devices are identical except that HI uses a different compound as a dopant. The current-voltage (J-V) characteristics of each OLED device were characterized by characterization equipment, while recording important parameters such as efficiency, lifetime, and external quantum efficiency, as shown in table 1.

TABLE 1

Through detection, the compounds DPI-1 to DPI-19 are adopted as dopants of the HTL layer, and the efficiency and the service life of the obtained device are obviously improved compared with those of the compound 1 in the comparative example.

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

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

Claims

1. An aromatic ring-fused cyclobutene organic compound is characterized in that the structure is shown as the general formula (I):

wherein:

R₁、R₂、R₃、R₄each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atomsThioalkoxy group having 1 to 20C atoms, branched alkyl group having 3 to 20C atoms, cyclic alkyl group having 3 to 20C atoms, branched alkoxy group having 3 to 20C atoms, cyclic alkoxy group having 3 to 20C atoms, branched thioalkoxy group having 3 to 20C atoms, cyclic thioalkoxy group having 3 to 20C atoms, silyl group, ketone group having 1 to 20C atoms, alkoxycarbonyl group having 2 to 20C atoms, aryloxycarbonyl group having 7 to 20C atoms, cyano group, carbamoyl group, haloformyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having from 6 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; two adjacent R₁With or without rings formed from each other.

2. An aromatic cyclobutene organic compound according to claim 1 wherein Ar is¹、Ar²Are each independently selected from

Wherein: y is selected from CR₅N, P or SiR₅；

R₅Each occurrence is independently selected from: H. d, straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atomsRadical, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having from 6 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 40 ring atoms, a substituted or unsubstituted heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems.

3. The aromatic cyclobutene organic compound of claim 2 wherein Ar is Ar¹、Ar²Each independently selected from the group consisting of:

wherein denotes a fused site.

4. An aromatic ring-fused cyclobutene organic compound according to any one of claims 1 to 3 wherein Ar is¹And Ar²Selected from the same group.

5. The aromatic-cyclo-butene organic compound according to claim 4, wherein the structure of the aromatic-cyclo-butene organic compound is represented by the general formula (II-1) or (II-2):

6. the aromatic-cyclo-butene organic compound according to claim 2, wherein the structure of the aromatic-cyclo-butene organic compound is any one of the structures represented by general formula (iii-1) and general formula (iii-6):

7. The aromatic-cyclo-butene organic compound according to any one of claims 1 to 6, wherein,

selected from any of the following structures:

R₆、R₇、R₈Each occurrence is independently selected from: H. d, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, a silyl group, a substituted ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a nitroso group, CF₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 carbon atoms, an aryloxy or heteroaryloxy group having 5 to 40 carbon atoms, or a combination thereof.

8. An aromatic-cyclo-butene organic compound according to claim 7 wherein G1 is selected from any one of the following groups:

9. an aromatic-cyclo-butene organic compound according to claim 2 wherein two adjacent R's are₁Can be mutually connected to form a ring system, and the structure of the aromatic ring-fused cyclobutene organic compound is shown as a general formula (IV-1) or (IV-2):

wherein Ar is³、Ar⁴Each independently selected from: a substituted or unsubstituted aromatic ring system having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic ring system having 5 to 10 ring atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, or an alicyclic group.

10. The aromatic cyclobutene organic compound of claim 9 wherein Ar is Ar³、Ar⁴Each independently selected from the group consisting of:

wherein:

denotes the fusion site;

X₁each occurrence is independently selected from CR₉Or N;

Y₁independently at each occurrence is selected from NR₁₀、CR₁₀R₁₁、SiR₁₀R₁₁、O、S、S(＝O)₂Or S (═ O);

R₉、R₁₀、R₁₁each occurrence is independently selected from: H. d, has 1A linear alkyl group of up to 20C atoms, an alkoxy group of 1 to 20C atoms, a thioalkoxy group of 1 to 20C atoms, a branched alkyl group of 3 to 20C atoms, a cyclic alkyl group of 3 to 20C atoms, a branched alkoxy group of 3 to 20C atoms, a cyclic alkoxy group of 3 to 20C atoms, a branched thioalkoxy group of 3 to 20C atoms, a cyclic thioalkoxy group of 3 to 20C atoms, a silyl group, a ketone group of 1 to 20C atoms, an alkoxycarbonyl group of 2 to 20C atoms, an aryloxycarbonyl group of 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, isothiocyanate, a hydroxyl group, a nitro group, a CF₃、OCF₃Cl, Br, F, a substituted or unsubstituted aromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms, a substituted or unsubstituted aryloxy group having from 5 to 40 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems; two adjacent R₉Form a ring or not form a ring; r₁₀、R₁₁With or without rings formed from each other.

11. A mixture comprising at least one of the aromatic ring-fused cyclobutene organic compounds of any one of claims 1 to 10 and at least one organic functional material selected from the group consisting of a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

12. A composition comprising at least one of an aromatic cyclo-butene organic compound according to any one of claims 1 to 10, a mixture according to claim 11, and at least one organic solvent.

13. An organic electronic device comprising at least one of the aromatic cyclo-butene organic compounds of claims 1 to 10, the mixture of claim 11 or prepared from the composition of claim 12.