CN111278892B - Polymers, mixtures, compositions containing amide bond groups and uses thereof - Google Patents

Abstract

The application provides a polymer containing an amide bond group, a mixture, a composition and an organic electronic device containing the polymer and application thereof. The polymer comprises a main chain structure connected by an amide bond and a functionalized side chain group; the polymer further comprises a crosslinkable group, and is crosslinked under the heating condition to form an insoluble and infusible polymer film, so that the polymer has excellent solvent resistance and is suitable for manufacturing complex multilayer organic electronic devices through solution processing. The application also relates to application of the polymer in photoelectric devices such as organic field effect transistors, organic light emitting diodes, polymer solar cells, perovskite solar cells and the like.

Description

Polymers, mixtures, compositions and applications thereof containing amide bond groups

This application claims the priority of Chinese patent application filed with the China Patent Office on December 28, 2017, with application number 201711461881.7 and invention name “Polymers containing amide bond groups and their applications in organic electronic devices”, the entire contents of which are incorporated by reference into this application.

Technical Field

The invention relates to the field of electroluminescent materials, and in particular to a polymer containing an amide bond group, a mixture, a composition and applications thereof.

Background Art

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

Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic electroluminescent elements that use organic electroluminescence usually have a structure with a positive electrode and a negative electrode and an organic layer between them. In order to improve the efficiency and life of the organic electroluminescent element, the organic layer has a multilayer structure, and each layer contains different organic substances. Specifically, it can include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In this organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, and electrons are injected from the negative electrode into the organic layer. When the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to the ground state. This organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

In order to realize efficient organic electroluminescent devices, in addition to developing high-performance luminescent materials, the efficient injection of electrons and holes from the cathode and anode respectively is the key. At present, most of the transmission materials are small molecule materials, which are suitable for the preparation of evaporation-type OLEDs. It is easy to prepare multi-layer, complex and efficient OLED devices through vacuum evaporation, but the production cost is expensive, time-consuming, and the material utilization rate is not high; especially for RGB side-by-side technology, it is difficult to realize the production of large-size displays due to the use of precision metal masks (FMM). In comparison, solution-processed OLEDs have the advantages of being able to prepare large-area, flexible devices through low-cost solution processing methods such as inkjet printing and printing, and have broad application prospects and commercial value.

Because general polymer photoelectric materials have similar intermiscible characteristics, i.e. polymer luminescent materials, hole injection/transmission materials, electron injection/transmission materials have good solubility in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran (THF) and other solvents, therefore when solution processing method prepares multilayer, complicated polymer light emitting diode, there are problems such as interface miscibility and interface erosion. In order to solve the interface erosion problem existing in solution processing, at present, by crosslinking method, i.e. development of crosslinkable polymer photoelectric materials, this material has excellent solubility before crosslinking, solution processing method film forming can be adopted, and then under conditions such as illumination, heat, etc., the crosslinking groups of the initiating polymer side chains react chemically with each other to form insoluble and infusible three-dimensional interpenetrating network polymers, with excellent solvent resistance, it is convenient to the solution processing preparation of subsequent functional layers (J.Mater.Chem.2008,18,4495). But the performance of solution processing OLED based on the crosslinked high polymer of these crosslinking groups has room for improvement. First, the existing cross-linkable polymers are all conjugated polymers with low triplet energy levels. When used for phosphorescent green light, they cannot play a good exciton blocking role, causing a decrease in efficiency. Secondly, the existing cross-linkable polymers themselves have limited stability, resulting in a short lifespan of OLED devices.

Therefore, new high-performance cross-linkable polymer charge transport materials need to be developed urgently.

Summary of the invention

Based on this, it is necessary to provide a polymer, mixture, composition and application thereof containing an amide bond group to solve the problems of low triplet state and poor stability of existing conjugated polymer transport materials and improve device performance.

The technical solution of the present invention is as follows:

A polymer as shown in general formula (I):

in:

o, p is the number of repetitions of the repeating unit, which is an integer greater than or equal to 1;

Ar ¹ and Ar ² are each independently selected from aromatic, heteroaromatic aromatic or heteroaromatic groups having 5 to 50 ring atoms, wherein the aromatic, heteroaromatic and non-aromatic groups are optionally further substituted with one or more R ¹ substituents;

^T1 and ^T2 are each independently an amide group; and when there are multiple ^T1s , the multiple ^T1s are the same or different, and when there are multiple ^T2s , the multiple ^T2s are the same or different;

a, b are each independently 0 or 1, and at least one of a and b is 1;

^R1 is selected from H, or D, or a straight-chain alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, or a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), an amide group (-C(=O)N(R) ₂ ), a haloformyl group, a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a _CF3 group , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

When there are multiple R ^1s , the multiple R ^1s are the same or different.

A mixture containing amide bond groups, comprising at least one of the above-mentioned polymers containing amide bond groups, and at least one other organic functional material, wherein the other organic functional material is selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials and organic dyes.

A composition comprises at least one of the above polymers containing amide bond groups or the above mixtures containing amide bond groups, and at least one organic solvent.

An organic electronic device comprises at least one of the above polymers containing amide bond groups or the above mixtures containing amide bond groups.

Since the polymer containing amide bond groups has a conjugated structural unit, the polymer is endowed with rich optical and electrical properties. The polymer material undergoes chemical reaction and cross-linking under heating conditions to generate an insoluble and infusible interpenetrating network polymer film, which has excellent solvent resistance and is suitable for making complex multi-layer organic electronic devices. Specifically:

(1) The polymer containing amide bond groups of the present invention, wherein the conjugated structural unit endows the polymer with rich optical (photoluminescence, electroluminescence, photovoltaic effect, etc.), electrical (semiconductor properties, carrier transport properties, etc.) and other properties, and its polymer properties also have good solubility and film-forming properties. Under heating conditions, the polymer can undergo chemical reactions to form a three-dimensional insoluble and infusible interpenetrating network polymer film with excellent solvent resistance. When preparing complex multi-layer optoelectronic devices, the solution processing characteristics of the polymer can be utilized to prepare polymer optoelectronic devices through solution processing techniques such as inkjet printing, screen printing, and spin coating, and the intermolecular crosslinking can be used to form an insoluble and infusible three-dimensional interpenetrating network polymer film with excellent solvent resistance, which is conducive to the solution processing of multi-layer polymer optoelectronic devices, especially organic electroluminescent devices.

(2) Compared with the conventional conjugated polymer optoelectronic materials with alternating carbon-carbon single and double bonds, the polymer containing amide bond groups of the present invention has a weaker conjugation ability of the amide groups, so that the lowest unoccupied molecular orbital (LUMO) and triplet energy level (ET) of the polymer are not greatly affected as the degree of polymerization increases, thereby helping to limit the excitons in the light-emitting layer, which is beneficial for the application in polymer optoelectronic devices, especially as a hole transport material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a structural diagram of a preferred light-emitting device according to the present invention, in which 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL) or a hole transport layer (HTL), 104 is a light-emitting layer, 105 is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.

DETAILED DESCRIPTION

The present invention provides a polymer containing an amide bond group and its application in an organic electronic device. In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

In the embodiments of the present invention, main body material, matrix material, host material and matrix material have the same meaning and can be interchangeable.

In the embodiments of the present invention, singlet state and singlet state have the same meaning and can be interchangeable.

In the embodiments of the present invention, triplet state and triplet state have the same meaning and can be interchangeable.

In the present invention, composition and printing ink, or ink have the same meaning and can be interchangeable.

Polymers include homopolymers, copolymers, and block copolymers. In the present invention, polymers also include 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.].

A conjugated polymer is a polymer whose main chain backbone is mainly composed of sp2 hybrid orbitals of C atoms. Famous examples include polyacetylene and poly(phenylenevinylene). The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp2 hybridization on the main chain is interrupted by some natural defects, it is still considered a conjugated polymer. In addition, the conjugated polymer in the present invention also includes aryl amine, aryl phosphine and other heteroaromatics, organometallic complexes, etc. on the main chain.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy levels ET, HOMO, and LUMO play a key role. The determination of these energy levels is introduced below.

HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level ET of the organic material can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 03W (Gaussian Inc.). The specific simulation method can be found in WO2011141110 or as described in the examples below.

It should be noted that the absolute values of HOMO, LUMO, and _ET depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as the starting point and the peak point on the CV curve, can give different HOMO/LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, and _ET are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

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

The present invention provides a polymer as shown in the general formula (I):

in:

o, p is the number of repetitions of the repeating unit, which is an integer greater than or equal to 1;

Ar ¹ and Ar ² are each independently selected from aromatic, heteroaromatic aromatic or heteroaromatic groups having 5 to 50 ring atoms, wherein the aromatic, heteroaromatic and non-aromatic groups are optionally further substituted with one or more R ¹ substituents;

^T1 and ^T2 are each independently an amide group; and when there are multiple ^T1s , the multiple ^T1s are the same or different, and when there are multiple ^T2s , the multiple ^T2s are the same or different;

a, b are each independently 0 or 1, and at least one of a and b is 1;

^R1 is selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, a thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a substituted or unsubstituted silyl group, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), an amide group (-C(=O)N(R) ₂ ), a haloformyl group, a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a _CF3 group , Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

When there are multiple R ^1s , the multiple R ^1s are the same or different.

In a preferred embodiment, the ^T1 and ^T2 comprise a structure as shown in the general formula (II):

Wherein: R ³ has the same meaning as R ¹ above.

In a more preferred embodiment, the ^T1 or ^T2 contains one or more of the following structural formulas:

n1 represents an integer from 0 to 30.

In certain embodiments, the polymer according to the present invention has a molecular weight Mw ≥ 10,000 g/mol, preferably ≥ 50,000 g/mol, more preferably ≥ 100,000 g/mol, even more preferably ≥ 150,000 g/mol, and most preferably ≥ 200,000 g/mol.

In a preferred embodiment, Ar ¹ and Ar ² are independently selected from aromatic or heteroaromatic groups with 6 to 50 ring atoms each time they appear; in a more preferred embodiment, Ar ¹ and Ar ² are independently selected from aromatic or heteroaromatic groups with 6 to 45 ring atoms each time they appear; in a very preferred embodiment, Ar ¹ and Ar ² are independently selected from aromatic or heteroaromatic groups with 6 to 40 ring atoms each time they appear; in a most preferred embodiment, Ar ¹ and Ar ² are independently selected from aromatic or heteroaromatic groups with 6 to 30 ring atoms each time they appear. One or more of these groups may be further substituted.

Aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic ring system or heteroaromatic group refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, and are particularly preferably selected from Si, N, P, O and/or S. These polycyclic rings can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purpose of the present invention, aromatic groups or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also, wherein multiple aromatic or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% 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 to be aromatic groups for the purposes of this invention.

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

Specifically, examples of heteroaromatic groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

In some preferred embodiments, according to the polymer of the present invention, the Ar1 has a π-conjugated structural unit with a larger energy gap, also called a backbone unit (Backbone Unit), preferably ≥2.2eV; more preferably ≥2.5eV; more preferably ≥3.0eV; most preferably ≥3.5eV.

In a preferred embodiment, the Ar ¹ comprises one or more combinations of the following structural groups:

Wherein: when there are multiple X, the multiple X are the same or different; the X is CR ⁴ or N;

When there are multiple Ys, the multiple Ys are the same or different; the Ys are CR ⁴ R ⁵ , SiR ⁴ R ⁵ , NR ⁴ , C(=O), S or O; R ⁴ , R ⁵ , and R ⁶ have the same meanings as R ¹ .

In certain preferred embodiments, according to the polymer of the present invention, wherein Ar ¹ or Ar ² can be the same or different when it appears multiple times and is selected from the following structural groups: cyclic aromatic groups, including benzene, biphenyl, triphenyl, benzo, fluorene, indolefluorene and its derivatives; aromatic heterocyclic groups, including triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole, pyridine indole, pyrrolodipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, oxathiazines, oxadiazines, indole, benzimidazole, indole azoles, indoxazine, bisbenzoxazoles, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazines, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, etc.

In other preferred embodiments, according to the polymer of general formula (I), Ar1 or Ar2, when present multiple times, may be selected from one or a combination of the following structural groups, which may be further substituted arbitrarily:

where u is 1 or 2 or 3 or 4.

Generally, the conjugated polymer contains at least one main chain structural unit. The main chain structural unit generally has a π-conjugated structural unit with a larger energy gap, also known as a backbone unit (Backbone Unit), which can be selected from monocyclic or polycyclic aromatic or heteroaromatic groups. In the present invention, the conjugated polymer can contain two or more main chain structural units. Generally, the content of the main chain structural unit is ≥40mol%, preferably ≥50mol%, more preferably ≥55mol%, and most preferably ≥60mol%.

In a preferred embodiment, according to the polymer of the present invention, Ar ¹ is a polymer main chain structural unit selected from benzene, biphenyl, triphenyl, benzo, fluorene, indolefluorene, carbazole, indolecarbazole, dibenzosilole, dithienocyclopentadiene, dithienosilole, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzoselenophene and their derivatives.

In a most preferred embodiment, Ar ¹ is selected from benzene, biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, fluorene, difluorene, spirobifluorene, p-phenylenevinylene, trans-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene and their derivatives.

In certain preferred embodiments, the polymers of the present invention have hole transport properties.

In certain preferred embodiments, according to the polymer of the present invention, the Ar ² has a π-conjugated structural unit with a smaller energy gap, preferably ≤3.5eV; more preferably ≤3.2eV; most preferably ≤3.0eV; the conjugated structure with a smaller energy gap in the polymer can make the polymer easier to generate charge under the action of an electric field.

In a preferred embodiment, according to the polymer of the present invention, wherein Ar ² is selected from units having hole transport properties, the preferred hole transport units can be selected from aromatic amines, triphenylamine, naphthylamine, thiophene, carbazole, dibenzothiophene, dithienocyclopentadiene, dithienosilole, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole and their derivatives.

In another preferred embodiment, Ar ² has a structure represented by Chemical Formula 1:

Ar1, Ar2, Ar3 can be selected independently in the same or different forms when they appear multiple times.

Ar1: is selected from a single bond, a mononuclear aromatic group, a polynuclear aromatic group, a mononuclear heteroaromatic group or a polynuclear heteroaromatic group, and the aromatic group or heteroaromatic group may be substituted by other side chains.

Ar2: is selected from mononuclear aromatic groups, polynuclear aromatic groups, mononuclear heteroaromatic groups or polynuclear heteroaromatic groups, and the aromatic groups or heteroaromatic groups may be substituted by other side chains.

Ar3: selected from mononuclear aromatic groups, polynuclear aromatic groups, mononuclear heteroaromatic groups or polynuclear heteroaromatic groups, and the aromatic groups or heteroaromatic groups may be substituted by other side chains. Ar3 may also be connected to other parts in Chemical Formula 1 through a bridging group.

n: is selected from 1, 2, 3, 4, or 5.

The preferred structural unit represented by Chemical Formula 1 is Chemical Formula 2

wherein Ar4, Ar6, Ar7, Ar10, Ar11, Ar13, Ar14 are defined as Ar2 in Chemical Formula 1,

Ar5, Ar8, Ar9, Ar12: are as defined by Ar3 in Chemical Formula 1.

Ar1-Ar14 in Chemical Formula 1 and Chemical Formula 2 are preferably selected from the following groups: phenylene, naphthalene, anthracene, fluorene, spirobifluorene, indenofuorene, phenanthrene, thiophene, pyrrole, carbazole, binaphthalene, dehydrophenanthrene, etc.

The structural units represented by Chemical Formula 1 and Chemical Formula 2 are particularly preferably selected from the following: each compound therein may be substituted by one or more substituents, and R is a substituent.

Table 1

R is selected from H, or D, or an aliphatic alkane containing 1 to 10 carbon atoms, an aromatic hydrocarbon, a substituted or unsubstituted aromatic ring or a heteroaromatic group containing 5 to 10 ring atoms. When there are multiple R, the multiple R are the same or different.

Further suitable units with hole transport properties correspond to hole transport materials small molecule hole transport materials (HTM). Suitable HTM materials may optionally include compounds having the following structural units: phthalocyanine, porphyrine, amine, aromatic amine, triarylamine, thiophene, fused thiophene (such as dithienothiophene and dibenzothiphene), pyrrole, aniline, carbazole, indolocarbazole, and their derivatives.

In certain particularly preferred embodiments, Ar ² comprises one or more combinations of the following structural groups:

wherein: Ar ³ -Ar ¹¹ , at each occurrence, is independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, one or more of which may be further substituted;

Preferably, Ar ³ -Ar ¹¹ , at each occurrence, are independently selected from an aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a non-aromatic group having 5 to 20 ring atoms, or a combination of these systems, one or more of which may be further substituted;

In certain preferred embodiments, the polymers of the present invention have electron transport properties.

In certain more preferred embodiments, according to the polymer of the present invention, wherein Ar2 is selected from units having electron transport properties, the preferred electron transport units may be selected from pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, oxathiazines, oxadiazines, indole, benzimidazole, indazole, indoxazine, bisbenzoxazoles, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazines, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine and derivatives thereof.

In principle, all electron transport materials ETM can be used as the unit with electron transport properties of the present invention. ETM is sometimes also called n-type organic semiconductor material. In principle, examples of suitable ETM materials are not particularly limited, and any metal complex or organic compound may be used as ETM as long as they can transport electrons. Preferred organic ETM materials can be selected from tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spiro-bifluorene, phenylene-vinylene, triazine, triazole, imidazole, pyrene, perylene, trans-indenofluorene, cis-indenonfluorene, dibenzol-indenofluorene, indenonaphthalene, benzanthracene and their derivatives.

On the other hand, the ^Ar2 having electron transport properties can be selected from a group having any skeleton in the following general formula:

Wherein: t represents an integer from 1 to 20;

^R7, at each occurrence, is independently selected from hydrogen, deuterium, a halogen atom (F, Cl, Br, I), a cyano group, an alkyl group, an alkoxy group, an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group or a heteroaryl group;

Each occurrence of X ₁ -X ₈ is independently selected from CR ⁸ or N, and at least one of them is N;

^M1 , ^M2 and ^M3 independently represent N( ^R8 ), C( ^R8 ) ₂ , Si( ^R8 ) ₂ , O, C=N( ^R8 ), C=C( ^R8 ) ₂ , P( ^R8 ), P(=O) ^R8 , S, S=O, _SO2 or none; ^Ar12 - ^Ar16 have the same meanings as ^Ar3 ; ^R8 has the same meanings as ^R1 .

In a particularly preferred embodiment, the polymer described in the present invention contains a crosslinkable group; the crosslinkable group is preferably selected from linear or cyclic alkenyl groups, linear diene groups, alkynyl groups, alkenyloxy groups, dieneoxy groups, acrylic groups, propylene oxide groups, butylene oxide groups, silane groups, and cyclobutane groups.

In a most preferred embodiment, the crosslinkable group is selected from one of the following structures:

The dotted line represents the position where the crosslinking monomer is bonded to other monomers in the polymer or functional groups on the monomers, and t and t1 represent integers greater than or equal to 0.

Ar ¹⁷ comprises an aromatic or heteroaromatic ring system having 5 to 40 ring atoms;

Each occurrence of R ⁹ to R ¹¹ is independently selected from the following groups: H, D, F, CN, alkyl chain, fluoroalkyl chain, aromatic ring, aromatic heterocycle, amino, silicon, germanyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl chain, deuterated partially fluorinated alkyl chain, deuterated aromatic ring, deuterated aromatic heterocycle, deuterated amino, deuterated silicon, deuterated germanyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, crosslinkable group. And adjacent R ⁹ , R ¹⁰ , R ¹¹ can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other or with the ring bonded to the group;

The crosslinkable group can appear in the polymer in various forms. Preferably, the crosslinkable group replaces each repeating unit on the polymer in the form of a substituent, such as the following general formula:

Wherein Q is a crosslinkable group as described above, Ar is a repeating unit on the polymer, and x is the molar fraction

In a preferred embodiment, the cross-linkable group is connected to Ar ¹ .

In another preferred embodiment, the crosslinkable group is connected to ^T1 or ^T2 .

In a most preferred embodiment, the crosslinkable group is attached to Ar ² .

In certain embodiments, the molar fraction x of the repeating unit comprising the crosslinkable group is: 0.02≤x≤0.30, preferably 0.05≤x≤0.25, more preferably 0.08≤x≤0.20, and most preferably 0.10≤x≤0.18.

In certain preferred embodiments, according to the polymer of general formula (I), the molar number of Ar ² having hole transport properties is yh, wherein 0.02≤yh≤0.30, preferably 0.05≤yh≤0.25, more preferably 0.08≤yh≤0.20, and most preferably 0.10≤yh≤0.18.

In other embodiments, according to the polymer of general formula (I), the molar number of Ar2 having electron transport properties is ye, wherein 0.02≤ye≤0.30, preferably 0.05≤ye≤0.25, more preferably 0.08≤ye≤0.20, and most preferably 0.10≤ye≤0.18.

In a preferred embodiment, the polymer of the present invention has |(HOMO-1)-HOMO|≥0.3eV, preferably ≥0.35eV, very preferably ≥0.4eV, more preferably ≥0.45eV, and most preferably ≥0.5eV, wherein HOMO represents the highest occupied molecular orbital of the polymer, and HOMO-1 represents the second highest occupied molecular orbital of the polymer.

In a preferred embodiment, the polymer according to the present invention has a relatively high LUMO, preferably LUMO ≥ -2.7 eV, more preferably ≥ -2.6 eV, more preferably ≥ -2.5 eV, most preferably ≥ -2.4 eV.

In certain preferred embodiments, the polymers according to the present invention have a relatively low HOMO, preferably a HOMO ≤ -5.0 eV, more preferably ≤ -5.1 eV, and most preferably ≤ -5.2 eV.

In certain preferred embodiments, the polymers according to the present invention have a large triplet energy level ET, preferably ET ≥ 2.5 eV, more preferably ≥ 2.6 eV, and most preferably ≥ 2.7 eV.

In a more preferred embodiment, the polymer according to the present invention is a conjugated polymer.

In one embodiment, in the general formula (I), a is 1, b is 1, o is 1, and p is 1;

In one embodiment, the polymer has a structural unit represented by any one of the following general formulas (II-1) to (II-10):

wherein R ¹¹ , R ¹² and R ¹³ are defined the same as R ³ ;

A is a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic group having 5 to 30 ring atoms;

L does not exist or is CH ₂ ;

W is O or S;

0<e<1, 0<f<1, and e+f=1.

In one embodiment, A in general formula (II-1) to general formula (II-10) is selected from the following groups:

wherein Y is CR ¹⁴ R ¹⁵ , SiR ¹⁴ R ¹⁵ , NR ¹⁴ , O, S or Se;

R ¹⁴ and R ¹⁵ are each independently H, C1-C20 alkyl, vinyl,

R ¹¹ is H, C1-C20 alkyl, vinyl, ethynyl, When there are multiple R ^11s , the multiple R ^11s are the same or different;

R ¹² and R ¹³ are each independently selected from the following groups: H, C1-C20 alkyl, 3-10 membered cycloalkyl, phenyl or

When there are a plurality of said R ¹² or R ¹³ , the plurality of said R ¹² or R ¹³ are the same or different.

In one embodiment, the polymer has a structural unit represented by the general formula (III-1):

R ¹⁴ and R ¹⁵ are each independently H or C1-C10 alkyl;

R ¹¹ is H, C1-C20 alkyl or vinyl; when there are multiple R ^11s , the multiple R ^11s are the same or different;

n is 1 or 2.

In one embodiment, the polymer has a structure shown in formula (III-2):

The R ¹⁶ and R ¹⁷ are each independently selected from: R ¹¹ is H, C1-C6 alkyl or vinyl, and the R ¹⁶ and R ¹⁷ are different.

Examples of polymers according to the present invention are listed below, but are not limited to:

The invention also relates to a method for synthesizing a polymer according to formula (I), wherein a raw material containing an active group is used for the reaction. The polymer can be obtained by polycondensation of at least one monomer containing a lactam, or an amine group and an acid group (including carboxylic acid, acyl halide, etc.), or at least two monomers containing a diamine and a dibasic acid group (including carboxylic acid, acyl halide, etc.) respectively.

The polymer of the present invention can be a homopolymer or a copolymer. The copolymer can be a random, alternating, block, comb or dendritic copolymer. The processes used to form polymers of these different structures are well known in the professional field, such as Priciples Of Polymerization, third edition, written by George Odian (John Wiley & Sons, New York, NY, 1991); Chemical Reactions of Natural and Synthetic Polymers, written by M. Lazer et al.; and Chemical Reactions on Polymers, written by Benham and Kinstle (1988).

The synthesis method of the polymer according to general formula (I) is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the glass transition temperature (Tg) of the polymer is ≥100°C, preferably ≥120°C, more preferably ≥140°C, even more preferably ≥160°C, and most preferably ≥180°C.

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

In a preferred embodiment, the weight average molecular weight (Mw) of the above polymer is preferably in the range of 10,000 to 1,000,000; more preferably 50,000 to 500,000; more preferably 100,000 to 400,000; even more preferably 150,000 to 300,000; and most preferably 200,000 to 250,000.

The present invention also provides a mixture, characterized in that it contains at least one of the above polymers and at least another organic functional material, wherein the at least another 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), light emitting material (Emitter), host material (Host) and organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

In a preferred embodiment, the mixture comprises a polymer according to the present invention and a fluorescent emitter (or a singlet emitter). The polymer according to the present invention can be used as the main body, wherein the weight percentage of the fluorescent emitter is ≤15wt%, preferably ≤12wt%, more preferably ≤9wt%, more preferably ≤8wt%, and most preferably ≤7wt%.

In certain embodiments, the mixture comprises a polymer according to the present invention, and a TADF material.

In another preferred embodiment, the mixture comprises a polymer according to the invention and a phosphorescent emitter (or triplet emitter). The polymer according to the invention can be used as the host, wherein the weight percentage of the phosphorescent emitter is ≤30 wt%, preferably ≤25 wt%, more preferably ≤20 wt%, and most preferably ≤18 wt%.

In other preferred embodiments, the mixture comprises a polymer according to the present invention, and a HTM material.

The following is a more detailed description of singlet emitters, triplet emitters and TADF materials (but not limited to this).

1. Singlet Emitter

Singlet emitters often have longer conjugated π electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019 and KR2006-0006760.

In a preferred embodiment, the singlet emitter can be selected from monostyrylamines, distyrylamines, tertiary styrylamines, tetrastyrylamines, styrylphosphines, styrylethers and aromatic amines.

A monostyrylamine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tertyrylamine is a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastyrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is diphenylethylene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to the amines. An arylamine or aromatic amine is a compound comprising three unsubstituted or substituted aromatic or heterocyclic ring systems directly attached to the 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 are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines. An aromatic anthraceneamine is a compound wherein one diarylamine group is directly attached to anthracene, preferably at the 9 position. An aromatic anthracenediamine is a compound wherein two diarylamine groups are directly attached to anthracene, preferably at the 9,10 positions. Aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines and aromatic chrysenediamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 positions of pyrene.

Examples, also preferred examples, of singlet emitters based on vinylamine and aromatic amines can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

Examples of singlet emitters based on stilbene and its derivatives are disclosed in US Pat. No. 5,121,029.

Further preferred singlet emitters can be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO 2008/006449, and dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Further preferred singlet emitters can be selected from fluorene-based fused ring systems, such as those disclosed in US2015333277A1, US2016099411A1, and US2016204355A1.

More preferred singlet luminophores can be selected from derivatives of pyrene, such as the structure disclosed in US2013175509A1; triarylamine derivatives of pyrene, such as the triarylamine derivatives of pyrene containing dibenzofuran units disclosed in CN102232068B; other triarylamine derivatives of pyrene with specific structures, such as those disclosed in CN105085334A and CN105037173A. Other materials that can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: anthracene such as 9,10-bis(2-naphthoanthracene), naphthalene, tetraphenyl, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacyclopentene, hexaphenylene, fluorene, spirobifluorene, Arylpyrene (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylene) -6- (4-dimethylaminophenylvinyl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) imine boron compounds (US 2007/0092753 A1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and dione pyrrolopyrroles. Some materials of singlet emitters can be found in the following patent documents: US 20070252517 A1, US4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

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

2. Triplet Emitter

Triplet emitters are also called phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex having the general formula M(L)u, wherein M is a metal atom, L can be the same or different each time it occurs, is an organic ligand, which is bonded or coordinated to the metal atom M through one or more positions, and u is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are linked to a polymer through one or more positions, preferably through an organic ligand.

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

Preferably, the triplet emitter contains a chelating ligand, ie a ligand which coordinates to the metal via at least two binding points, and it is particularly preferred that the triplet emitter contains two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine derivatives, 2(1-naphthyl)pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, by fluorine-containing or trifluoromethyl groups. Auxiliary ligands may be preferably selected from acetic acid acetone or picric acid.

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

Wherein M is a metal selected from transition metal elements or lanthanide or actinide elements, particularly preferably Ir, Pt, Au;

Ar ₁ may be the same or different each time it appears, and is a cyclic group, which contains at least one donor atom, that is, an atom with a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinated and connected to the metal; Ar ₂ may be the same or different each time it appears, and is a cyclic group, which contains at least one C atom, through which the cyclic group is connected to the metal; Ar ₁ and Ar ₂ are linked together by covalent bonds, and may each carry one or more substituents, and they may also be linked together through substituents; L' may be the same or different each time it appears, and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q may be 0, 1, 2 or 3, preferably 2 or 3; p may be 0, 1, 2 or 3, preferably 1 or 0.

Examples of materials and applications of some triplet emitters can be found in the following patent documents and literature: WO200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, Baldo, Thompson et al. Nature 403, (2000), 750-753, US 20090061681 A1, US20090061681 A1, Adachi et al.Appl.Phys.Lett .78(2001), 1622-1624, J. Kido et al. 96, 1974, 998, Ma et al., Synth.Metals 94, 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US20010053462A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, W02012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1, WO The entire contents of the above-listed patent documents and literature are hereby incorporated herein by reference.

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

3. Thermally activated delayed fluorescence (TADF):

Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). Although phosphorescent materials can effectively utilize singlet excitons and triplet excitons formed by electrical excitation to emit light due to the strong spin-orbit coupling of the heavy atom center, the internal quantum efficiency of the device can reach 100%. However, the expensive phosphorescent materials, poor material stability, and serious device efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence luminescent materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. This type of material generally has a small singlet-triplet energy level difference (ΔE _st ), and triplet excitons can be transformed into singlet excitons through anti-intersystem crossing. This can make full use of singlet excitons and triplet excitons formed under electrical excitation. The internal quantum efficiency of the device can reach 100%. At the same time, the material structure is controllable, the properties are stable, the price is cheap, and no precious metals are required, and the application prospects in the field of OLED are broad.

TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second best ΔEst < 0.25 eV, more preferably ΔEst < 0.20 eV, and most preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558 (A), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), Adachi, et.al. Adv. 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.Nature Photonics, 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.Mate r., 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, the entire contents of the above-listed patents or article documents are hereby incorporated into this article by reference.

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

In other embodiments, the solubility of the polymer according to the present invention in toluene at 25°C is ≥5 mg/ml, preferably ≥7 mg/ml, and most preferably ≥10 mg/ml.

According to a composition of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or borate or phosphate compounds, or a mixture of two or more solvents.

In a preferred embodiment, according to a composition of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents.

Examples of aromatic or heteroaromatic solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, 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, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, ethyl 2-furoate, etc.;

Examples of aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;

Examples of aromatic ether-based solvents suitable for the present invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethyl ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

In some preferred embodiments, according to the composition of the present invention, the at least one organic 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, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, 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, etc.

In other preferred embodiments, according to the composition of the present invention, the at least one organic solvent can be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate, etc. are particularly preferred.

The solvent may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises a polymer or a mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of the other organic solvent include (but are 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, tetralin, decalin, indene and/or mixtures thereof.

In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having a Hansen solubility parameter within the following ranges:

δ _d (dispersion force) is in the range of 17.0 to 23.2 MPa ^1/2 , especially in the range of 18.5 to 21.0 MPa ^1/2 ;

δ _p (polar force) is in the range of 0.2 to 12.5 MPa ^1/2 , especially in the range of 2.0 to 6.0 MPa ^1/2 ;

δ _h (hydrogen bonding force) is in the range of 0.9 to 14.2 MPa ^1/2 , and particularly in the range of 2.0 to 6.0 MPa ^1/2 .

According to the composition of the present invention, the organic solvent should be selected considering its boiling point parameter. In the present invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; more preferably ≥250°C; most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head. The organic solvent can be evaporated from the solvent system to form a film containing a functional material.

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

Among them, suitable printing or coating techniques include (but are not limited to) inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. Preferred are gravure printing, screen printing and inkjet printing. Gravure printing and inkjet printing will be applied in the embodiments of the present invention. The solution or suspension may further include one or more components such as surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing technology and its related requirements for related solutions, such as solvents and concentrations, viscosity, etc., please refer to the "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

The preparation method as described above is characterized in that the thickness of the formed functional layer is 5nm-1000nm.

The present invention further relates to an organic electronic device, comprising at least one polymer or a mixture as described above. The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEECs), organic field effect transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diodes), etc., and organic electroluminescent devices such as OLEDs, OLEECs and organic light emitting field effect transistors are particularly preferred.

In some particularly preferred embodiments, the electron transport layer or the hole transport layer of the electroluminescent device comprises a polymer or a mixture as described above.

The present invention further comprises a method for preparing a functional layer of an organic electronic device comprising the polymer of the present invention, comprising at least the following steps:

The first step is to dissolve the polymer of the present invention in an organic solvent or a mixed solvent to prepare a solution;

Step 2: coating the solution on a functional layer of the device by printing or coating, wherein the printing or coating method can be selected from, but not limited to, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc.;

Step 3: Heat-treating the obtained film at a temperature of at least 100 degrees Celsius, optionally with ultraviolet light, to cause a cross-linking reaction and solidify the film.

Optional step: washing the cross-linked and cured film with an organic solvent to remove residual compounds that have not been cross-linked and cured.

In certain embodiments, the thickness of the obtained cross-linked and cured film (after solvent cleaning) is at least 50%, preferably at least 60%, more preferably at least 70%, and most preferably at least 85% of the thickness of the film before cross-linking and curing.

The light emitting device described above, especially OLED, comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. For example, see 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. It is best that the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics, and its glass transition temperature Tg is above 150°C, preferably above 200°C, more preferably above 250°C, and preferably above 300°C. Examples of suitable flexible substrates include poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode may include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting body in the light-emitting layer or the p-type semiconductor material as the HIL or HTL or the electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and 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), etc. Other suitable anode materials are known and can be easily selected for use by a person skilled in the art. The anode 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), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore in the light-emitting layer or the n-type semiconductor material as the electron injection layer (EIL) or the electron transport layer (ETL) or the hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as cathodes of OLEDs may be used as cathode materials for the device of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material 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), etc.

OLEDs may also include other 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), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

According to the light emitting device of the present invention, the light emission wavelength is between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

The present invention also relates to the application of the electroluminescent device 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 in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware 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.

Specific embodiments

1. Polymer Synthesis

Example 1: Synthesis of polymer P1

Synthesis of intermediate 2

Compound 1 (7.03 g, 10 mmol) was dissolved in 80 ml of acetic acid in a 250 ml round-bottom flask, and 80 ml of fuming nitric acid and 20 ml of concentrated sulfuric acid were added dropwise. The mixture was stirred and heated to 90 °C under a nitrogen atmosphere. The reaction was allowed to react for 15 h. After cooling, the reactant was poured into ice water. The product was extracted with dichloromethane. The organic phase was washed with a saturated solution of NaHCO ₃ , saturated brine and water in sequence. The solvent was evaporated and dried to obtain a crude product. Intermediate 2 was obtained by chromatography, with a weight of 4.83 g and a yield of 61%.

Synthesis of intermediate 3

The intermediate 2 (1.59 g, 2 mmol) was dissolved in 50 ml of ethanol under nitrogen protection, and then hydrazine monohydrate (1.02 g, 20 mmol) and palladium carbon (0.1 g (10% w/w)) were added, stirred, and refluxed for 2 h. After the reaction was completed, the filtrate was extracted with dichloromethane, and the organic phase was washed with saturated brine and water, and dried to obtain a crude product. Intermediate 3 was obtained by chromatography, weighing 1.24 g, with a yield of 85%.

Synthesis of intermediate 4

Aniline (0.93 g, 0.01 mol) and ethyl 4-bromobenzoate (4.58 g, 0.02 mol), sodium tert-butyl alcohol (8.45 g, 0.088 mol), and catalyst bis(dibenzylideneacetone)palladium (1.27 g, 0.0022 mol) were added to a two-necked bottle, and dry toluene was used as the reaction solvent. The mixture was deoxygenated by blowing nitrogen for 30 min, and then 13 ml of tri-tert-butylphosphine was added. The reaction progress was tracked, and water was added to terminate the reaction after the reaction was completed. The mixture was extracted with ethyl acetate, and the organic phase was evaporated to remove the solvent. Silica gel was added and mixed with powder and sampled on a silica gel column to obtain the product intermediate 4, which weighed 2.95 g and had a yield of 76%.

Synthesis of intermediate 5

Under nitrogen protection, add 5 ml of freshly distilled DMF (64 mmol) to a 50 ml three-necked flask. Slowly add 6 ml of phosphorus oxychloride (64 mmol) under ice bath and stir rapidly. After the phosphorus oxychloride is dripped, slowly add 55 ml of DMF solution of intermediate 4 (8.95 g, 23 mmol). After the dripping is completed, heat to 35-40 ° C under nitrogen protection and stir overnight. The resulting solution is poured into 200 ml of water. After filtration, the resulting filter cake is recrystallized from ethanol to obtain intermediate 5, weighing 9.20 g, with a yield of 96%.

Synthesis of intermediate 6

In an ice bath and under nitrogen protection, potassium tert-butoxide (2.24g, 20mmol), methyltriphenylphosphonium bromide (4.28g, 12mmol) and 40mL freshly distilled tetrahydrofuran were added to a dry 250 ml two-necked flask. After stirring for half an hour, a 20ml tetrahydrofuran solution of intermediate 5 (4.17g, 10mmol) was added, and after dripping, the mixture was slowly warmed to room temperature and stirred for 4 hours under nitrogen protection. After adding water to quench the reaction, it was extracted with petroleum ether and dried over anhydrous sodium sulfate. Column chromatography with petroleum ether as the developing agent gave intermediate 6, weighing 2.49g, with a yield of 60%.

Synthesis of intermediate 7

Intermediate 6 (0.415 g, 1 mmol) was dissolved in 6 ml of methanol, and 7 ml of (6 M) sodium hydroxide aqueous solution was added. After reacting at room temperature for 2 h, hydrochloric acid was added to pH = 1, extracted with ethyl acetate and washed with saturated brine. After drying, the solvent was removed in vacuo. The obtained solid was dissolved in 20 ml of anhydrous dichloromethane, 0.34 ml (4 mmol) of oxalyl chloride was added under nitrogen protection, and a catalytic amount of DMF was dropped. The reaction was stirred at room temperature for 2 h, and the solvent was removed in vacuo to obtain intermediate 7, weighing 0.18 g, with a yield of 46%.

Synthesis of polymer P1

Under nitrogen protection, intermediate 3 (733 mg, 1 mmol) and intermediate 7 (396 mg, 1 mmol) were added to a 25 mL reaction bottle and dissolved in 10 ml DMAc. The mixture was stirred at room temperature for 12 h. The solution was poured into a large amount of water, the precipitate was filtered, washed with methanol and acetone, and dried in vacuo to obtain polymer P1, weighing 898 mg.

Example 2: Synthesis of polymer P2

Synthesis of intermediate 8

4-tert-butylaniline (1.49 g, 0.01 mol) and ethyl 4-bromobenzoate (4.58 g, 0.02 mol), sodium tert-butyl alcohol (8.45 g, 0.088 mol), and catalyst bis(dibenzylideneacetone)palladium (1.27 g, 0.0022 mol) were added to a two-necked bottle, and dry toluene was used as the reaction solvent. The mixture was deoxygenated by nitrogen bubbling for 30 min, and then 13 ml of tri-tert-butylphosphine was injected. The reaction process was tracked. After the reaction was completed, water was added to terminate the reaction, and the mixture was extracted with ethyl acetate. The organic phase was evaporated to remove the solvent, and silica gel was added to mix the powder and sampled on a silica gel column to obtain the product intermediate 8, which weighed 3.69 g and had a yield of 83%.

Synthesis of intermediate 9

Intermediate 8 (0.445 g, 1 mmol) was dissolved in 6 ml of methanol, and 7 ml of (6 M) sodium hydroxide aqueous solution was added. After reacting at room temperature for 2 h, hydrochloric acid was added to pH = 1, extracted with ethyl acetate and washed with saturated brine. After drying, the solvent was removed. The resulting solid was dissolved in 20 ml of anhydrous dichloromethane, oxalyl chloride (0.34 ml, 4 mmol) was added under nitrogen protection, and a catalytic amount of DMF was added dropwise. The reaction was stirred at room temperature for 2 h, and the solvent was removed in vacuo to obtain intermediate 9, weighing 0.22 g, with a yield of 51%.

Synthesis of polymer P2

Under nitrogen protection, intermediate 3 (733 mg, 1 mmol), intermediate 7 (119 mg, 0.3 mmol) and intermediate 9 (298 mg, 0.7 mmol) were added to a 25 mL reaction bottle and dissolved in 10 ml DMAc. The reaction was stirred at room temperature for 12 h. The solution was poured into a large amount of water, the precipitate was filtered, washed with methanol and acetone, and dried in vacuo to obtain polymer P2, weighing 761 mg.

Example 3: Synthesis of polymer P3

Under nitrogen protection, compound a (370 mg, 1 mmol) and compound b (141 mg, 1 mmol) were dissolved in anhydrous dichloromethane, and 22 ml of 1-hydroxybenzotriazole solution (1 M, DMF/ _{CH2Cl2 ,} 1:1) and 20 ml of dicyclohexylcarbodiimide solution (1 M, _CH2Cl2 ) were added under ice bath. The reaction was stirred at room temperature for 2 days, the precipitate was filtered, the filtrate was vacuum dried _, the solid was dissolved in dichloromethane, washed with 10% _NaHCO3 aqueous solution, and dried to obtain polymer P3, weighing 327 mg.

2. Energy level structure of compounds

The energy structure of organic small molecules can be obtained by quantum calculation, for example, using TD-DFT (time-dependent density functional theory) through Gaussian03W (Gaussian Inc.), and the specific simulation method can be found in W02011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet), 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" and the basis set "6-31G(d)" (Charge 0/Spin Singlet).

For conjugated polymers, the energy structure of the polymer can be obtained by calculating the trimer. For example, the energy level of the compound P1 obtained by polymerizing the monomers M1 and M2 as shown below is calculated by the trimer M1-M2-M1 and/or M2-M1-M2, in which the alkyl chains are all substituted with methyl groups.

Trimer M1-M2-M1:

Trimer M2-M1-M2:

The HOMO and LUMO energy levels calculated above are calculated according to the following calibration formula, and S1 and T1 are used directly.

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

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

HOMO(G) and LUM0(G) are the direct calculation results of Gaussian 09W, in eV. The results are shown in Table 1, where ΔHOMO = HOMO-(HOMO-1):

3. Preparation method of OLED devices

Among them, H1 is a co-host material, and its synthesis refers to the Chinese patent application number CN201510889328.8; H2 is a co-host material, and its synthesis refers to patent W0201034125A1; E1 is a phosphorescent guest, and its synthesis refers to patent CN102668152; Comp A to Comp C and Poly-TFB are device HTL comparison materials, among which the synthesis of Comp A, Comp B and Comp C is similar to the similar structural compound of this patent; Poly-TFB (CAS: 223569-31-1) was purchased from Lumtec.Corp.

The device structure of the OLED device (OLED-Ref) is: ITO/PEDOT:PSS (80nm)/Poly-TFB (20nm)/EML/cathode; the preparation steps of the OLED device (OLED-Ref) are as follows:

1) Cleaning of the ITO transparent electrode (anode) glass substrate: ultrasonic treatment with an aqueous solution of 5% Decon90 cleaning solution for 30 minutes, followed by ultrasonic cleaning with deionized water for several times, ultrasonic cleaning with isopropanol, and drying with nitrogen; treatment under oxygen plasma for 5 minutes to clean the ITO surface and improve the work function of the ITO electrode;

2) Preparation of HIL and HTL: PEDOT:PSS (Clevios ^TM PEDOT:PSS Al4083) was spin-coated on a glass substrate treated with oxygen plasma to obtain an 80 nm film, which was then annealed in air at 150°C for 20 min. A 20 nm Poly-TFB film (5 mg/mL toluene solution) was then spin-coated on the PEDOT:PSS layer and subsequently treated on a hot plate at 180°C for 60 min.

3) Preparation of the light-emitting layer: H1, H2, and E1 were first dissolved in toluene at a weight ratio of 40:40:20. The concentration of the solution was 20 mg/mL. The solution was spin-coated in a nitrogen glove box to obtain a 60 nm thin film, which was then annealed at 120° C. for 10 minutes.

4) Cathode preparation: Place the spin-coated device into a vacuum evaporation chamber, and sequentially evaporate 2 nm of barium and 100 nm of aluminum to complete the light-emitting device.

5) All devices were packaged with UV-curable resin and glass cover in a nitrogen glove box.

The preparation steps of other OLED devices (OLED-1 to OLED-3 and OLED-A to OLED-C) are the same as above, but when preparing the HTL layer, P1 to P3 and Comp A to Comp C are used to replace Poly-TFB, respectively, and after cross-linking and curing, they are rinsed twice with toluene and then the film thickness is measured.

The current-voltage characteristics, luminous intensity and external quantum efficiency of the device were measured by a Keithley 236 current-voltage measurement system and a calibrated silicon photodiode.

HTL thickness (nm) Efficiency (cd/A)@1000nits relative to OLED-Ref OLED-Ref 20 1 OLED-1 20 1.33 OLED-2 20 1.57 OLED-3 20 1.45 OLED-A 20 1.02 OLED-B 20 0.85 OLED-C 20 0.94

When the polymer according to the present invention is used in HTL, the performance, especially the efficiency, of other comparative devices is greatly improved. This may be due to two reasons. First, the polymer HTM containing amide bond groups according to the present invention has a higher triplet energy level, thus having a better blocking effect on triplet states; second, the polymer containing amide bond groups according to the present invention has good solubility and is suitable for solution processing. At the same time, the insolubility after cross-linking and curing is also suitable for subsequent processing.

It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims (7)

1. An amide bond group-containing polymer, characterized in that the polymer contains a structural unit represented by any one of the general formulae (II-3), (II-7) to (II-10):

Wherein R is ¹¹ 、R ¹² And R is ¹³ Each independently selected from H or C1-C20 alkyl;

a is a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic group having 5 to 30 ring atoms;

l is absent, or CH ₂ The method comprises the steps of carrying out a first treatment on the surface of the 0 < e < 1,0 < f < 1, and e+f=1.

2. The polymer of claim 1, having a structure represented by the general formula (III-3):

n is an integer greater than or equal to 1.

3. The polymer of any one of claims 1-2, wherein the polymer has a i (HOMO-1) -HOMO i.gtoreq.0.3 eV, wherein HOMO represents the highest occupied orbital of the polymer and HOMO-1 represents the second highest occupied orbital of the polymer.

4. A mixture comprising at least one polymer according to any one of claims 1 to 3, and at least one further organic functional material, which can be selected from hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials or organic dyes.

5. A composition comprising at least one polymer according to any one of claims 1 to 3 or a mixture according to claim 4, and at least one organic solvent.

6. An organic electronic device comprising at least one polymer according to any one of claims 1 to 3 or a mixture according to claim 4.

7. The organic electronic device of claim 6, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode.