CN108137604B - Azole derivatives and their use in organic electronic devices - Google Patents

Abstract

The present invention discloses a pyrrole derivative and its application in organic electronic devices, especially in organic light-emitting diodes. The pyrrole derivatives have structural features as shown in the general formula (I), and these compounds have good rigidity, chemical and thermal stability, so they can effectively improve the color purity, stability, luminous efficiency of the compounds and the performance of the corresponding devices. performance. By further optimizing the device structure and changing the concentration of the pyrrole derivative in the matrix, the best device performance can be achieved, and an OLED device with high efficiency, high brightness and high stability can be realized, which provides a better material option for full-color display and lighting applications.

Description

Pyrrole Derivatives and Their Applications in Organic Electronic Devices

technical field

The present invention relates to a pyrrole derivative and its application in organic electronic devices, especially in organic light-emitting diodes. The present invention also relates to an organic electronic device, especially a light-emitting element, comprising such a lop-pyrrole derivative, and its application in displays and lighting devices.

Background technique

Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat-panel displays and lighting due to their synthetic diversity, relatively low fabrication cost, and excellent optical and electrical properties of organic semiconductor materials.

In order to improve the luminous efficiency of organic light-emitting diodes, various luminescent material systems based on fluorescence and phosphorescence have been developed, and the development of excellent blue light materials is a huge challenge whether it is fluorescent materials or phosphorescent materials. The organic light-emitting diode of the blue fluorescent material used is more reliable. Nevertheless, the emission spectrum of most blue fluorescent materials is too broad and the color purity is poor, which is not conducive to high-end display, and the synthesis of such fluorescent materials is also complicated, which is not conducive to mass production. The stability of OLED needs to be further improved. Therefore, the development of blue fluorescent materials with narrow-band emission spectrum and good stability is conducive to obtaining blue light devices with longer life and higher efficiency on the one hand, and improving the color gamut on the other hand, thereby improving the display effect.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the object of the present invention is to provide a class of pyrrole derivatives, which can effectively improve the color purity, stability, luminescence of the compounds because of their good rigidity, chemical and thermal stability. Efficiency and corresponding device performance.

The technical solution of the present invention is: a pyrrole derivative containing the structure of general formula (I):

Wherein, Ar ¹ , Ar ² in each occurrence can be the same or different from unsubstituted or R ¹ -substituted aromatic hydrocarbons or heteroaromatic hydrocarbon systems;

R ¹ is selected from H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , straight chain alkanes, alkane ethers, containing 1 to 10 carbon atoms alkane sulfide or branched alkane or cycloalkane,; each group may be replaced by one or more reactive groups R, and one or more non ^- adjacent methylene groups may be replaced by : R ² C=CR ² , C=C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, C=N(R ² ), O, S, -COO-, or CONR ² , in which one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or N ₂ , or by containing one or more reactive groups group R ² , an aromatic group or a heteroaromatic substituted aromatic amine, or a substituted or unsubstituted carbazole;

R ² in each occurrence, the same or different, is H, D, aliphatic alkanes containing 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic rings containing 5 to 10 ring atoms or heteroaromatic groups.

In some of these embodiments, the pyrrole derivatives are preferably selected from the following general formula:

Wherein, R3 represents -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , straight chain alkane, alkane Ethers, any of alkane sulfides or branched alkanes or cycloalkanes containing 1 to 10 carbon atoms, and aryl groups containing 6 to 10 carbon atoms;

x is any of the numbers 0-4, y is any of the numbers 0-5, z is any of the numbers 0-7, u is any of the numbers 0-8, v is any of the numbers 0-9 Any of the numbers, w is any of the numbers 0-11;

L is a linking group, independently selected from a single bond or any one of B1 to B4:

wherein, R ³ to R ²⁶ are selected from -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , Any of straight chain alkanes, alkane ethers, alkane sulfides containing 1 to 10 carbon atoms or branched alkanes or cycloalkanes, and aryl groups containing 6 to 10 carbon atoms.

In some of these embodiments, the pyrrole derivative is characterized in that it is selected from the following general formula:

In some of these embodiments, the lopyrrole derivatives, wherein Ar ² in the general formula (I), (I-1)-(I-10) is an unsubstituted or substituted aromatic ring unit, in Multiple occurrences may be independently selected from any one of the general formulae C1 to C10:

wherein, R ²⁷ to R ¹⁰⁶ are selected from -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , Any of straight chain alkanes, alkane ethers, alkane sulfides containing 1 to 10 carbon atoms or branched alkanes or cycloalkanes, and aryl groups containing 6 to 10 carbon atoms.

In some of these embodiments, the lopyrrole derivatives are characterized in that Ar ² in the general formula (I), (I-1)-(I-10) is independently selected from:

The present invention also provides a high polymer comprising a repeating unit including a structural unit represented by the general formula (I).

The present invention also provides a mixture comprising one of the above-mentioned lopyrrole derivatives or high polymers and at least one organic functional material. The organic functional material can be selected from hole injection material (HIM), hole transport material (HTM), electron transport material (ETM), electron injection material (EIM), electron blocking material (EBM), hole blocking material ( HBM), luminescent material (Emitter), host material (Host) and organic dyes, etc.

The present invention also provides a composition comprising a lopyrrole derivative or high polymer according to the present invention, and at least one organic solvent.

The present invention also provides an application of the lopyrrole derivatives or high polymers according to the present invention in organic electronic devices.

The present invention also provides an organic electronic device comprising at least one lopyrrole derivative or high polymer according to the present invention or a mixture thereof.

In some embodiments, the organic electronic device can be selected from organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors , Organic lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes (Organic PlasmonEmitting Diode), especially organic light emitting diodes (OLEDs).

Preferably, in some of the embodiments, the organic electronic device is an organic electroluminescence device, which comprises at least one light-emitting layer, and the light-emitting layer comprises a pyrrole derivative or a polymer according to the present invention thing.

Compared with the prior art, the beneficial effects of the present invention:

The present invention provides a class of pyrrole derivatives, such compounds have good rigidity, chemical and thermal stability, and thus can effectively improve the color purity, stability, luminous efficiency and performance of corresponding devices of the compounds. By further optimizing the device structure and changing the concentration of the pyrrole derivative in the matrix, the best device performance can be achieved, and an OLED device with high efficiency, high brightness and high stability can be realized, which provides a better material option for full-color display and lighting applications.

Detailed ways

The present invention provides a novel pyrrole derivative, the corresponding mixture and composition, and its application in organic electronic devices. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention is further described below in detail. . It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

In the present invention, compositions and printing inks, or inks, have the same meaning and are interchangeable between them.

In the present invention, host material, matrix material, Host or Matrix material have the same meaning and can be interchanged among them.

In the present invention, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and can be interchanged.

The present invention relates to an isopyrrole derivative represented by the following general formula (I):

Wherein, Ar ¹ , Ar ² in each occurrence can be the same or different from unsubstituted or R ¹ -substituted aromatic hydrocarbons or heteroaromatic hydrocarbon systems;

R ¹ is selected from H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , straight chain alkanes, alkane ethers, containing 1 to 10 Carbon atom alkane sulfide or branched alkane or cycloalkane,; each group may be substituted by one or more reactive groups R ² , and one or more non-adjacent methylene groups (CH ₂ ) may be replaced by The following group substitutions: R ² C=CR ² , C=C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, C =N(R ² ), O, S, -COO-, or CONR ² , where one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or N ₂ , or by including one or A plurality of reactive groups R ² , an aromatic group or a heteroaromatic substituted aromatic amine is replaced, or is replaced by a substituted or unsubstituted carbazole;

R ² in each occurrence, the same or different, is H, D, aliphatic alkanes containing 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic rings containing 5 to 10 ring atoms or heteroaromatic groups.

In certain preferred embodiments, the lopyrrole derivatives according to general formula (I), wherein Ar ¹ and Ar ² can be selected from unsubstituted or substituted aromatic rings or heterocyclic rings having 2 to 20 carbon atoms Aromatic ring.

In a preferred embodiment, the aromatic ring system contains 5-15 carbon atoms in the ring system, more preferably 5-10 carbon atoms, the heteroaromatic ring system contains 2-15 carbon atoms in the ring system, more preferably Preferably 2 to 10 carbon atoms, and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 4. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S.

Aromatic ring systems or aromatic groups refer to hydrocarbon groups containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. A heteroaromatic ring system or heteroaromatic group refers to a hydrocarbon group (containing a heteroatom) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, ie, fused rings. Of these ring species that are polycyclic, at least one is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only systems of aryl or heteroaryl groups, but also systems in which multiple aryl or heteroaryl groups can 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). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diarylether, etc., are also considered to be aromatic ring systems for the purpose of the 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, azole, diazole, thiazole, tetrazole, indole, carbazole, Pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisazole, benisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, Pyrimidine, triazine, quinoline, isoquinoline, naphthalene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.

In a preferred embodiment, said Ar ¹ -Ar ² with general formula (I) can be selected from one of the following general formulas:

wherein, X is independently selected from CR ₁ or N, and at least one of them is N;

Y is selected from CR ₂ R ₃ , SiR ₂ R ₃ , NR ₂ , C(=O), S, or O;

R ₁ , R ₂ , R ₃ are H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched group having 3 to 20 C atoms Chain or cyclic alkyl, alkoxy or thioalkoxy groups or silyl groups, or substituted keto groups having 1 to 20 C atoms, having 2 to 20 C atoms alkoxycarbonyl groups, aryloxycarbonyl groups with 7 to 20 C atoms, cyano groups (-CN), carbamoyl groups (-C(=O) _NH2 ), halomethyl groups Acyl group (-C(=O)-X where X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate groups, hydroxyl groups, nitro groups, _CF3 groups, Cl, Br, F, crosslinkable groups or substituted or unsubstituted aryl groups with 5 to 40 ring atoms An aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the groups R ₁ , R ₂ , R ₃ can be The rings bonded to each other and/or to said groups form monocyclic or polycyclic aliphatic or aromatic ring systems.

In some preferred embodiments, R ₁ , R ₂ , R ₃ are H, or D, or a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 10 C atoms, or have Branched or cyclic alkyl, alkoxy or thioalkoxy groups of 3 to 10 C atoms or silyl groups, or substituted keto groups of 1 to 10 C atoms , alkoxycarbonyl groups with 2 to 10 C atoms, aryloxycarbonyl groups with 7 to 10 C atoms, cyano groups (-CN), carbamoyl groups (-C(= O) _NH2 ), haloformyl group (-C(=O)-X where X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate group groups, thiocyanate groups or isothiocyanate groups, hydroxyl groups, nitro groups, _CF3 groups, Cl, Br, F, crosslinkable groups or with 5 to 20 rings Atom-substituted or unsubstituted aromatic or heteroaromatic ring systems, or aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems, in which one or more groups R ₁ , R ₂ , R ₃ may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the group is bonded.

In certain preferred embodiments, Ar and Ar in general ^formula ( ^I ) may be selected from the following structural units, which may be further substituted:

In other more preferred embodiments, Ar ¹ and Ar ² in the general formula (I) can be selected from the following structural units, which can be further substituted:

In other more preferred embodiments, according to general formula (I) of the pyrrole derivatives, wherein Ar ² is selected from unsubstituted or substituted aromatic rings with 5 to 20 ring atoms, excluding heteroaromatic clan ring.

In a more preferred embodiment, the pyrrole derivatives according to the present invention are selected from the following general formula:

Wherein, R3 represents -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , straight chain alkane, alkane Ethers, any of alkane sulfides or branched alkanes or cycloalkanes containing 1 to 10 carbon atoms, and aryl groups containing 6 to 10 carbon atoms;

x is any of the numbers 0-4, y is any of the numbers 0-5, z is any of the numbers 0-7, u is any of the numbers 0-8, v is any of the numbers 0-9 Any of the numbers, w is any of the numbers 0-11;

L is a linking group, independently selected from a single bond or any one of B1 to B4:

wherein, R ³ to R ²⁶ are selected from -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , Any of straight chain alkanes, alkane ethers, alkane sulfides containing 1 to 10 carbon atoms or branched alkanes or cycloalkanes, and aryl groups containing 6 to 10 carbon atoms.

In some preferred embodiments, in the above-mentioned pyrrole derivatives, Ar ² is an unsubstituted or substituted aromatic ring unit, which can be independently selected from the general formulae C1 to C10 when it occurs multiple times. Either of:

wherein, R ²⁷ to R ¹⁰⁶ are selected from -H, -F, -Cl, Br, I, -D, -CN, -NO ₂ , -CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , Any of straight chain alkanes, alkane ethers, alkane sulfides containing 1 to 10 carbon atoms or branched alkanes or cycloalkanes, and aryl groups containing 6 to 10 carbon atoms.

Specific examples of suitable isopyrrole derivatives according to the present invention are given below, but are not limited to:

In certain embodiments, the ep-pyrrole derivatives according to the present invention have an emission wavelength between 300 and 800 nm, preferably between 350 and 600 nm, more preferably between 400 and 500 nm.

In some preferred embodiments, the isopyrrole derivatives according to the present invention have higher photoluminescence quantum efficiency, generally ≥ 15%, preferably ≥ 25%, more preferably ≥ 35%, and optimally ≥ 50%.

The glass transition temperature of the pyrrole derivatives according to the present invention is ≥100°C, preferably ≥110°C, more preferably ≥120°C, most preferably ≥140°C.

The present invention also relates to a high polymer, wherein at least one repeating unit comprises the structure represented by the general formula (I). In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit represented by general formula (I) is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

The present invention still further relates to a mixture comprising at least one lopyrrole derivative or high polymer according to the present invention, and at least one other organic functional material.

Another organic functional material described here, including hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM), electron Blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescence emitters), thermally activated delayed fluorescence emitters (TADF), triplet emitters (phosphorescence emitters), especially luminescent metal organic complexes substances, and organic dyes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents are hereby incorporated by reference.

Organic functional materials can be small molecules or high polymer materials.

The term "small molecule" as defined herein refers to molecules that are not polymers, oligomers, dendrimers, or blends. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤3000 g/mol, preferably ≤2000 g/mol, most preferably ≤1500 g/mol.

High polymer, namely Polymer, includes homopolymer (homopolymer), copolymer (copolymer), mosaic copolymer (block copolymer). In addition, in the present invention, the high polymer also includes dendrimers. For the synthesis and application of dendrimers, please refer to [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 high polymer, its main chain (backbone) is mainly composed of sp ² hybrid orbitals of C atoms, famous examples are: polyacetylene and poly(phenylenevinylene), which The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp ² hybridization on the main chain is interrupted by some natural defects, it is still considered as a conjugated polymer. In addition, the conjugated high polymer of the present invention also includes aryl amine, aryl phosphine and other heteroaromatics (heteroarmotics), metal organic complexes (organometallic complexes) on the main chain. )Wait.

In certain embodiments, in the mixture according to the present invention, the content of the pyrrole derivative is 0.01 to 50 wt%, preferably 0.1 to 40 wt%, more preferably 0.2 to 30 wt%, and most preferably 2 to 15wt%.

In a preferred embodiment, the mixture according to the invention comprises an lopyrrole derivative according to the invention and another organic functional material, wherein the lopyrrole derivative has a lower singlet energy level than the other organic functional material The singlet energy level of the functional material, but the triplet energy level of the pyrrole derivative is higher than that of another organic functional material.

In a preferred embodiment, the mixture according to the invention comprises a lopyrrole derivative or polymer according to the invention and a singlet matrix material.

In another preferred embodiment, the mixtures according to the invention comprise an epazopyrrole derivative or polymer according to the invention, a singlet host material and a further singlet emitter.

In another preferred embodiment, the mixture according to the present invention comprises an epazopyrrole derivative or polymer according to the present invention and a TADF material.

The singlet host materials, singlet emitters and TADF materials are described in more detail below (but not limited thereto).

1. Singlet Host:

Examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the emitter, especially the singlet emitter or fluorescent emitter.

Examples of organic compounds used as singlet matrix materials can be selected from the group consisting of ring-containing aromatic hydrocarbon compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenanthrene, fluorene, pyrene, chrysanthemum, Heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridineindole, Pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine , oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenepyridine, thiophenedipyridine, benzofuran Selenophenypyridines and selenophenodipyridines; groups containing 2 to 10 ring structures, which may be of the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, directly with each other or through at least one of the following groups Linked together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and alicyclic groups.

In a preferred embodiment, the singlet matrix material can be selected from compounds comprising at least one of the following groups:

In the above-mentioned groups, R ¹ can be independently selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; Ar ¹ is aryl or heteroaryl; n is an integer from 0 to 20; X ¹ -X ⁸ are selected from CH or N; X ⁹ and X ¹⁰ are selected from CR ¹ R ² or NR ¹ . R ² can be independently selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl

Some examples of anthracene-based singlet host materials are listed in the table below:

2. Singlet Emitter

Singlet emitters tend to have longer conjugated pi electron systems. To date, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, and indenofluorenes and its derivatives disclosed in WO2008/006449 and WO2007/140847.

In a preferred embodiment, the singlet emitter may be selected from the group consisting of monostyrylamines, di-styrylamines, tristyrylamines, tetrastyrylamines, styryl phosphines, styryl ethers and aromatic amines.

A monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrylamine refers to a compound containing three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to amines. Arylamine or aromatic amine refers to a compound containing three unsubstituted or substituted aromatic or heterocyclic ring systems directly attached to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic drolidines and aromatic dridodiamines. An aromatic anthraceneamine refers to a compound in which a divalent arylamine group is attached directly to the anthracene, preferably in the 9 position. An aromatic anthracene diamine refers to a compound in which two divalent arylamine groups are attached directly to the anthracene, preferably in the 9,10 position. Aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrene diamines, and aromatic pyrene diamines are similarly defined, with the divalent arylamine group preferably attached to the 1 or 1,6 position of the pyrene.

Examples of singlet emitters based on vinylamines and aromatic amines, which are also preferred, can be found in the following patent documents: WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006/210830A, EP1957606A1 and US2008/0113101A1, the entire contents of the above-listed patent documents are hereby incorporated by reference.

Examples of singlet emitters based on stilbene and its derivatives are US5121029.

Further preferred singlet emitters can be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO2006/122630, benzoindenofluorene-amines and benzoindenofluorene-diamines, Dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO2008/006449, as disclosed in WO2007/140847.

Other materials useful as singlet emitters Polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-bis(2-naphthanthracene), naphthalene, tetraphenyl, xanthene, phenanthrene , pyrene (such as 2,5,8,11-tetra-t-butyl), indenopyrene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1, 1'-biphenyl), diindenopyrene, decacycloene, hexabenzone, fluorene, spirobifluorene, arylpyrene (eg US20060222886), arylene vinylene (eg US5121029, US5130603), cyclopentadiene Such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4(dicyanomethylene)-6-(4-p-dimethylaminostyrene) yl-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compound (US2007/0092753A1), bis(azinyl)methylene compound, carbostyryl compound, oxazine Ketones, benzoxazoles, benzothiazoles, benzimidazoles and diketopyrrolopyrroles. Materials for some singlet emitters can be found in the following patent documents: US20070252517A1, US4769292, US6020078, US2007/0252517A1, US2007/0252517A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the table below:

3. Thermally activated delayed fluorescence light-emitting material (TADF):

Traditional organic fluorescent materials can only use 25% of singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent materials enhance intersystem crossing due to the strong spin-orbit coupling in the heavy atom center, the singlet and triplet excitons formed by electrical excitation can be effectively used to emit light, and the internal quantum efficiency of the device can reach 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. Thermally activated delayed fluorescence light-emitting materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be transformed into singlet excitons through inverse intersystem crossing to emit light. This can take full advantage of the singlet and triplet excitons formed under electrical excitation. The internal quantum efficiency of the device can reach 100%.

The TADF material needs to have a small singlet-triplet energy level difference, generally ΔEst<0.3eV, preferably ΔEst<0.2eV, more preferably ΔEst<0.1eV, and most preferably ΔEst<0.05eV. In a preferred embodiment, the TADF has better 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), WO2013154 A1), Adachi, et.al.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. Commun., 48, 2012, 11392, Adachi, et. al. NaturePhotonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012 , 234, Adachi, et.al.J.Am.Chem.Soc, 134, 2012, 14706, Adachi, et.al.Angew.Chem.Int.Ed, 51, 2012, 11311, Adachi, et.al.Chem .Commun., 48, 2012, 9580, Adachi, et.al.Chem.Commun., 48, 2013, 10385, Adachi, et.al.Adv.Mater., 25, 2013, 3319, Adachi, et.al. Adv.Mater., 25, 2013, 3707, Adachi, et.al.Chem.Mater., 25, 2013, 3038, Adachi, et.al.Chem.Mater., 25, 2013, 3766, Adachi, et.al .J.Mater.Chem.C.,1,2013,4599,Adachi,et.al.J.Phys.Chem.A.,117,2013,5607, all of the above-listed patent or article documents are hereby incorporated The contents are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below:

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

In certain embodiments, the lopyrrole derivatives according to the present invention have a molecular weight of ≥ 700 g/mol, preferably ≥ 800 g/mol, and most preferably ≥ 900 g/mol.

In other embodiments, the lopyrrole derivatives according to the present invention have a solubility in toluene of ≥2 mg/ml, preferably ≥3 mg/ml, and most preferably ≥5 mg/ml at 25°C.

The present invention further relates to a composition or ink comprising a lopyrrole derivative or polymer according to the invention or a mixture as described above, and at least one organic solvent.

The present invention further provides a film prepared from solution comprising the lopyrrole derivative or polymer according to the present invention.

When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of suitable inks are suitable for specific substrates and specific printing methods.

In a preferred embodiment, the ink according to the present invention has a surface tension in the range of about 19 dyne/cm to 50 dyne/cm at operating temperature or at 25°C; more preferably in the range of 22 dyne/cm to 35 dyne/cm; most preferably is in the range of 25dyne/cm to 33dyne/cm.

In another preferred embodiment, the viscosity of the ink according to the present invention at operating temperature or 25°C is about 1 cps to 100 cps; preferably 1 cps to 50 cps; more preferably 1.5 cps to 20 cps; most The good is in the 4.0cps to 20cps range. Compositions so formulated will be suitable for ink jet printing.

The viscosity can be adjusted by different methods, such as by suitable solvent selection and concentration of functional materials in the ink. According to the ink containing the dipyrrole derivative or high polymer according to the present invention, it is convenient for people to adjust the printing ink in an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition according to the present invention is in the range of 0.3% to 30% by weight, preferably in the range of 0.5% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, and even better It is in the range of 0.5% to 10% by weight, and preferably in the range of 1% to 5% by weight.

In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, especially aliphatic chain/ring substituted aromatic solvents, or aromatic ketones solvent, or aromatic ether solvent.

Examples of solvents suitable for the present invention are, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylene Naphthalene, 3-isopropylbiphenyl, p-cymene, dipentylbenzene, tripentylbenzene, amyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetratoluene, 1,2,3,5-tetratoluene, 1,2,4,5-tetratoluene, butylbenzene, dodecylbenzene, diphenylbenzene Hexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-cymene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene , Diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl base) pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetrahydronaphthalene Ketone, 2-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, isophor Erone, 2,6,8-trimethyl-4-nonanone, fecalone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, fo Erketone, di-n-amyl ketone; Aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy -2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy toluene, 4-ethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, acrylonitrile Glyceryl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2 -Phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, amyl ether, c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol Alcohol 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; Ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyllactone, oleic acid Alkyl esters, etc.

Further, according to the ink of the present invention, the at least one solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5 -Hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, amyl ether, hexyl ether, dioctyl ether, ethylene glycol Alcohol 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, etc.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent, including (but not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine , toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydro Naphthalene, decalin, indene and/or mixtures thereof.

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

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

The invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferred is a preparation method by printing or coating.

Among them, suitable printing or coating techniques include (but are not limited to) ink jet printing, jet printing (Nozzle Printing), letterpress printing, screen printing, dip coating, spin coating, blade coating, roll printing, twist roll printing , offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slit extrusion coating, etc. Preferred are ink jet printing, slot extrusion coating, jet printing and gravure printing. The solution or suspension may additionally contain one or more components such as surface-active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders, etc., to adjust viscosity, film-forming properties, improve adhesion, and the like. For detailed information on printing technology and its related requirements for the solution, such as solvent and concentration, viscosity, etc., please refer to the "Handbook of PrintMedia: Technologies and Production Methods" edited by Helmut Kipphan (Handbook of PrintMedia: Technologies and Production Methods) , ISBN 3-540-67326-1.

The present invention also provides the application of the above-mentioned lopyrrole derivative or high polymer in organic electronic devices. The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors, organic Lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes (Organic Plasmon Emitting Diode), etc., especially OLED. In the embodiment of the present invention, the lopyrrole derivative is preferably used in the light-emitting layer of the OLED device.

The present invention further relates to an organic electronic device comprising at least one of the above-mentioned lopyrrole derivatives or high polymers. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one of the above-mentioned pyrrole derivatives or polymers . The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors, organic Lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes (Organic Plasmon Emitting Diode).

In a particularly preferred embodiment, the organic electronic device is an electroluminescent device, especially an OLED, which comprises a substrate, an anode, at least a light-emitting layer, and a cathode.

The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting device. See, eg, Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably the substrate has a smooth surface. Substrates free of surface defects are particularly desirable. In a preferred embodiment, the substrate is flexible, optionally a polymer film or plastic, with a glass transition temperature Tg above 150°C, preferably above 200°C, more preferably above 250°C, most preferably over 300°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 the hole injection layer (HIL) or hole transport layer (HTL) or light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light-emitting layer or the p-type semiconductor material as a HIL or HTL or electron blocking layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. 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 those 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.

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 emissive layer. In one embodiment, the work function of the cathode and the LUMO level of the emitter in the emissive layer or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, more preferably less than 0.2 eV. In principle, all materials that can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, _LiF /Al, MgAg alloys, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can 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.

OLEDs can also contain other functional layers such as hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), hole blocking layer (HBL).

In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer of the light-emitting layer comprises the lopyrrole derivative of the present invention, and is prepared by vacuum evaporation or solution processing, preferably vacuum evaporation.

In a preferred embodiment, in the electroluminescent device according to the present invention, the hole transport layer thereof comprises the deuterated triarylamine derivative of the present invention.

In another preferred embodiment, in the electroluminescent device according to the present invention, the light-emitting layer thereof comprises the high polymer of the present invention and is prepared by solution processing.

The electroluminescent device according to the present invention has an emission wavelength between 300 and 800 nm, preferably between 350 and 650 nm, more preferably between 400 and 625 nm.

The present invention also relates to the use of organic electronic devices according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The present invention will be described below with reference to the preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should It is recognized that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

1. Pyrrole derivatives and their energy structures

The energy levels of the pyrrole derivatives B-1-B-7 can be obtained by quantum calculation, such as Gaussian03W (Gaussian Inc.) using TD-DFT (time-dependent density functional theory). For the specific simulation method, please refer to WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/SpinSinglet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is calculated by the TD-DFT (time-dependent density functional theory) method "TD-SCF/DFT/Default Spin/B3PW91/6-31G/d" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the calibration formula below, and S1 and T1 are used directly.

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

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

Where HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1:

Table I

2. Synthesis of pyrrole derivatives

2.1 Synthesis Example 1: Synthesis of Compound B-1

In a dry two-necked flask, place benzaldehyde (21.2g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), 3-methylaniline (21.4g, 200mmol), then add 700mL of glacial acetic acid, stir a little 2,3-Butanedione (8.6 g, 100 mmol) was then added, and the reaction was stirred at 100 °C for 3 hours, cooled to room temperature, added with water, extracted with dichloromethane, then dried, concentrated, and diluted with dichloromethane/petroleum ether=1 /5 was passed through the column to obtain B-1 (14.1 g).

2.2 Synthesis Example 2: Synthesis of Compound B-2

In a dry two-necked flask, place 4-bibenzaldehyde (36.4g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), aniline (18.6g, 200mmol), then add 700mL of glacial acetic acid, after a little stirring 2,3-Butanedione (8.6 g, 100 mmol) was added, and the reaction was stirred at 100° C. for 3 hours, cooled to room temperature, added with water, extracted with dichloromethane, then dried, concentrated, and diluted with dichloromethane/petroleum ether=1/ 5 was passed through the column to obtain B-2 (17.8 g).

2.3 Synthesis Example 3: Synthesis Compound B-3

In a dry two-necked flask, place 4-biphenylaldehyde (36.4g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), 3-methylaniline (21.4g, 200mmol), then add 700mL of glacial acetic acid, After a little stirring, 2,3-butanedione (8.6 g, 100 mmol) was added, and then the reaction was stirred at 100 °C for 3 hours, cooled to room temperature, added water, extracted with dichloromethane, then dried, concentrated, and washed with dichloromethane/petroleum Ether=1/5 Column passed to give B-3 (18.6g).

2.4 Synthesis Example 4: Synthesis of Compound B-4

In a dry two-necked flask, place benzaldehyde (21.2g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), 4-benzidine (33.8g, 200mmol), then add 700mL of glacial acetic acid, after a little stirring 2,3-Butanedione (8.6 g, 100 mmol) was added, and the reaction was stirred at 100° C. for 3 hours, cooled to room temperature, added with water, extracted with dichloromethane, then dried, concentrated, and diluted with dichloromethane/petroleum ether=1/ 5 was passed through the column to give B-4 (17.8 g).

2.5 Synthesis Example 5: Synthesis of Compound B-5

In a dry two-necked flask, place 4-bibenzaldehyde (36.4g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), 4-benzidine (33.8g, 200mmol), then add 700mL of glacial acetic acid, slightly After stirring, 2,3-butanedione (8.6 g, 100 mmol) was added, and then the reaction was stirred at 100 °C for 3 hours, cooled to room temperature, added water, extracted with dichloromethane, then dried, concentrated, and washed with dichloromethane/petroleum ether. = 1/5 passed through column to give B-5 (22.38g).

2.6 Synthesis Implementation Example 6:

Synthesis of intermediate 6-a:

2-Bromo-9,9-dimethylfluorene (2.73 g, 10 mmol) was added to 100 mL of THF solution under nitrogen to dissolve, then 6 mL of n-butyllithium (2M, 15 mmol) was added at -78°C, and the reaction was incubated 1 hour, then dry DMF (2.5 mL, 32 mmol) was added dropwise, then warmed to room temperature, the reaction was continued to stir for 2 hours, concentrated, added water, extracted with dichloromethane, concentrated, then ethyl acetate/petroleum ether=1 /10 was passed through the column to give 6-a (1.77g).

Synthesis of compound B-6:

In a dry two-necked flask, place 6-a (44.4g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), aniline (18.6g, 200mmol), then add 700mL of glacial acetic acid, add 2 , 3-Butanedione (8.6g, 100mmol), then stirred at 100°C for 3 hours, cooled to room temperature, added water, extracted with dichloromethane, then dried, concentrated, washed with dichloromethane/petroleum ether=1/5 The column yielded B-6 (20.22 g).

2.7 Synthesis Example 7: Synthesis of Compound B-7

In a dry two-necked flask, place 6-a (44.4g, 200mmol), p-toluenesulfonic acid (6.88g, 40mmol), 3-methylaniline (21.4g, 200mmol), then add 700mL of glacial acetic acid, add a little After stirring, 2,3-butanedione (8.6 g, 100 mmol) was added, and the reaction was stirred at 100° C. for 3 hours, cooled to room temperature, added with water, extracted with dichloromethane, then dried, concentrated, and diluted with dichloromethane/petroleum ether= 1/5 was passed through the column to give B-7 (21.06g).

3. Preparation and characterization of OLED devices:

The fabrication steps of OLED devices with ITO/NPD(60nm)/15%B-1～B-7:ADN(15nm)/TPBi(65nm)/LiF(1nm)/Al(150nm)/cathode are as follows:

a. Cleaning of the conductive glass substrate: when it is used for the first time, it can be cleaned with a variety of solvents, such as chloroform, ketone, isopropanol, and then subjected to ultraviolet ozone plasma treatment;

b. HTL (60nm), EML (25nm), ETL (65nm): thermally evaporated in high vacuum (1×10 ^-6 mbar, mbar);

c. Cathode: LiF/Al (1nm/150nm) thermally evaporated in high vacuum (1×10 ^-6 mbar);

d. Encapsulation: The device is encapsulated with UV-curable resin in a nitrogen glove box.

The current-voltage-luminance (JVL) characteristics of each OLED device were characterized by characterizing the device while recording important parameters such as efficiency and external quantum efficiency. After testing, the maximum external quantum efficiency of OLEDx (corresponding to the pyrrole derivative B-x) reached more than 4%.

Further optimization, such as device structure optimization, HTM, ETM and host material combination optimization, will further improve device performance, especially efficiency, driving voltage and lifetime.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are more specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (9)

1. An organic electronic device, characterized in that the organic electronic device is an organic electroluminescent device comprising at least a light-emitting layer comprising a pyrrole derivative represented by the following general formula (I-3):

l is a single bond or

Ar²Independently at multiple occurrences, is selected from any one of the general formulae (C1) to (C2):

R²⁷to R³⁸Selected from-H, -F, -Cl, Br, I, -D, -CN, -NO₂，-CF₃Any one of a straight-chain alkyl group, an alkoxy group, an alkylthio group having 1 to 10 carbon atoms, a branched-chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group having 6 to 10 carbon atoms.

2. The organic electronic device of claim 1, wherein R is²⁷-R³⁸Is selected from-H or-CH₃。

3. The organic electronic device according to claim 1, wherein formula (I-3) is selected from the following formulae:

4. the organic electronic device of claim 1, wherein the Ar is selected from the group consisting of²Independently at multiple occurrences, are selected from formula (C1).

5. The organic electronic device of claim 1, wherein R is²⁷-R³⁸Are all-H.

6. The organic electronic device of claim 1, whereinR is²⁷-R³⁸In which one is selected from-CH₃And the rest are-H.

7. The organic electronic device according to claim 1, wherein the general formula (I-3) is a general formula (B-6):

8. the organic electronic device according to claim 1, wherein the general formula (I-3) is a general formula (B-7):

9. an organic electronic device, wherein the organic electronic device is an organic electroluminescent device comprising at least one light-emitting layer, wherein the light-emitting layer comprises a polymer;

the polymer comprises a repeating unit comprising a structural unit represented by the general formula (I-3) according to any one of claims 1 to 8.