CN111344289A - Nitrogen-containing heterocyclic compound, high polymer, mixture, composition and application thereof - Google Patents

Abstract

The invention relates to a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition and application thereof, wherein the nitrogen-containing heterocyclic compound has a structure shown as a chemical formula (1):

Description

Nitrogen-containing heterocyclic compound, high polymer, mixture, composition and application thereof

The present application claims priority from the chinese patent office filed on 27/12/2017, entitled "a nitrogen-containing heterocyclic compound and its use" under the patent application number 201711451351.4, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to nitrogen-containing heterocyclic compounds, high polymers, mixtures, compositions and application thereof.

Background

Organic semiconductor materials have a wide variety of synthetic, relatively low manufacturing costs and excellent optical and electrical properties, and Organic Light Emitting Diodes (OLEDs) have great potential for use in optoelectronic devices such as flat panel displays and lighting.

To date, a luminescent material system based on fluorescence and phosphorescence has been developed, and an organic light emitting diode using a fluorescent material has a high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1: 3. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency. However, the stability of phosphorescent OLEDs is still to be improved. The stability of OLEDs, in addition to the emitter itself, is critical for the host material.

For red and green light phosphorescence emitting devices, the phosphorescence host material of the light emitting layer is mainly some carbazole organic compounds, and due to the defects of insufficient structural rigidity and the like, the stability of the host material is limited, so that the service life of the device is short. In order to further improve the stability of the host material, the japan university of kyoto (WO2012118164) fixes three benzene rings of triarylamine by two ether chains, and obtains better device results, but the lone pair of electrons of the oxygen atom still causes insufficient stability of the material. In 2011, japan materials corporation (JP5724588B2) synthesized that the benzene ring of one triarylamine is fixed by a single bond, but the conjugation range is still small, so that the rigidity is small, and the benzene rings of the other triarylamines can still rotate, so that the stability of the main material is still insufficient. In JP2016219487A, JP2012234873A, the rotation of three benzenes on triarylamines is limited by introducing six-membered rings or heteroatoms, but the lifetime of OLED devices prepared as phosphorescent host materials still needs to be further improved.

Therefore, there is still a need for improvement and development of new materials for overcoming the problem of insufficient stability and rigidity of the current phosphorescent host luminescent materials.

Disclosure of Invention

In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition and a use thereof, and aims to solve the problems of insufficient stability and rigidity of the conventional phosphorescent host luminescent material.

The technical scheme of the invention is as follows:

a nitrogen-containing heterocyclic compound having a structure represented by formula (1):

wherein:

Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶and Ar⁷Each independently selected from: aromatic, heteroaromatic or nonaromatic ring systems having 5 to 20 ring atomsAromatic, heteroaromatic or nonaromatic ring systems optionally further substituted by one or more R¹Substituted by groups;

l1, L2, L3, L4, L5 and/or L6 are absent or each independently selected from: straight-chain, branched-chain and cyclic alkyl radicals having 1 to 15C atoms, aromatic, heteroaromatic or nonaromatic ring systems having 5 to 20 ring atoms;

Y₁、Y₂、Y₃、Y₄、Y₅and/or Y₆Is absent, or is each independently selected from a single bond, a di-bridge or a tri-bridge group, and Y is₁、Y₂、Y₃、Y₄、Y₅And Y₆Is connected with three adjacent groups by single bond or double bond;

when said Y is₁、Y₂、Y₃、Y₄、Y₅Or Y₆When it is a single bond or a di-bridging group, with said Y₁、Y₂、Y₃、Y₄、Y₅Or Y₆The linked L is absent;

when there are more than one R¹When a plurality of R¹Same or different, said R¹Selected from H, F, Cl, Br, I, D, CN, -NO₂、CF₃、B(OR²)₂、Si(R²)₃A straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, an alkylether group or an alkylether group containing 1 to 10 carbon atoms;

R²selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy group having 3 to 20C atoms, a thioalkoxy group having 3 to 20C atoms, a silyl group, a substituted keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a,Nitro radical, CF₃A group, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms; and R is²The radicals in (a) may be bonded to one another and/or to the ring to which they are attached to form a mono-or polycyclic, aliphatic or aromatic ring system;

R³is as defined for R²；

n is 0,1 or 2;

m is 0,1 or 2.

A nitrogen-containing heterocyclic polymer whose repeating unit comprises the structure of the above nitrogen-containing heterocyclic compound.

The nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer and at least one organic functional material are selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting body or a host material.

A nitrogen-containing heterocyclic composition, which comprises the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer and at least one organic solvent.

An organic electronic device comprising at least one of the above-mentioned nitrogen-containing heterocyclic compound or the above-mentioned nitrogen-containing heterocyclic polymer.

The nitrogen-containing heterocyclic compound, the high polymer, the mixture and the composition are simple to synthesize, the benzene rings of the two triarylamines are fixed by using N atoms, the rigidity of material molecules is improved conveniently, the stability of the material is improved, the light-emitting device is prepared by using the nitrogen-containing heterocyclic compound, the high polymer, the mixture and the composition, and the service life of the device is prolonged. The nitrogen-containing heterocyclic compound, the high polymer, the mixture and the composition can be used as red and green phosphorescent host materials, and can improve the luminous efficiency and the service life of the electroluminescent device by being matched with a proper guest material, thereby providing a solution of the luminescent device with low manufacturing cost, high efficiency, long service life and low roll-off.

Detailed Description

The present invention provides a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition and use thereof, and the present invention will be described in further detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

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

In the present invention, the Host material, Matrix material, Host or Matrix material have the same meaning and are interchangeable with each other.

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

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

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy level ET1, HOMO, LUMO, plays a key role. The determination of these energy levels is described below.

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

The triplet energy level ET1 of the organic material may be measured by low temperature Time resolved luminescence spectroscopy, or may be obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods may be found in WO2011141110 or as described in the examples below.

It should be noted that the absolute values of HOMO, LUMO, ET1 depend on the measurement or calculation method used, and even for the same method, different methods of evaluation, e.g. starting point and peak point on the CV curve, may give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, ET1 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 level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

The invention provides a nitrogen-containing heterocyclic compound shown as a chemical formula (1):

wherein:

Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶and Ar⁷Each independently selected from: an aromatic, heteroaromatic or non-aromatic ring system having 5 to 20 ring atoms, optionally further substituted by one or more R¹Substituted by groups;

l1, L2, L3, L4, L5 and/or L6 are absent or each independently selected from: linear, branched and cyclic alkanes having 1 to 15 carbon atoms, aromatic, heteroaromatic or nonaromatic ring systems having 5 to 20 ring atoms;

Y₁、Y₂、Y₃、Y₄、Y₅and/or Y₆Is absent, or is each independently selected from a single bond, a di-bridge or a tri-bridge group, and Y is₁、Y₂、Y₃、Y₄、Y₅And Y₆Is connected with three adjacent groups by single bond or double bond;

when said Y is₁、Y₂、Y₃、Y₄、Y₅Or Y₆When it is a single bond or a di-bridging group, with said Y₁、Y₂、Y₃、Y₄、Y₅Or Y₆The linked L is absent;

when there are more than one R¹When a plurality of R¹Same or different, said R¹Selected from H, F, Cl, Br, I, D, CN, NO₂、 CF₃、B(OR²)₂、Si(R²)₃Straight-chain alkane, branched-chain alkane, cycloalkane, alkane ether or alkane thioether containing 1-10 carbon atoms;

R²selected from H, D, straight chain alkyl groups having 1 to 20C atoms, alkoxy groups having 1 to 20C atoms, thioalkoxy groups having 1 to 20C atoms, branched or cyclic alkyl groups having 3 to 20C atoms, alkoxy groups having 3 to 20C atoms, thioalkoxy groups having 3 to 20C atoms, silyl groups, substituted keto groups having 1 to 20C atoms, alkoxycarbonyl groups having 2 to 20C atoms, aryloxycarbonyl groups having 7 to 20C atoms, cyano groups (-CN), carbamoyl groups (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A group, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms; and R is²The radicals in (a) may be bonded to one another and/or to the ring to which they are attached to form a mono-or polycyclic, aliphatic or aromatic ring system;

R³is as defined for R²；

n is 0,1 or 2;

m is 0,1 or 2.

At one endIn the examples, Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently selected from: an aromatic or heteroaromatic ring having 5 to 20 ring atoms, optionally further substituted by one or more R¹And (4) substituting the group.

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

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

Specifically, examples of the fused heterocyclic aromatic group are: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

In one embodiment, the compound according to the present invention, Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently is a group comprising at least one of the following structures:

wherein:

when there are plural X's in the same group, each X is independently selected from N or CR₅；

When there are plural Y's in the same group, each Y is independently CR₆R₇，SiR₆R₇，NR₆Or, C (═ O), S, or O;

R₅、R₆、R₇is as defined for R²。

In one embodiment, the Ar is¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently is a group comprising at least one of the following structures, wherein H on the ring may be optionally substituted:

in one embodiment, the Ar is¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently selected from the group consisting of:

in one embodiment, Y₁、Y₂、Y₃、Y₄、Y₅And Y₆Identical or different at each occurrence is a single bond or a two-or three-bridged radical.

In one embodiment, the di-or tri-bridging group is selected from the following groups:

wherein:

R⁹、R¹⁰and R¹¹Definitions of the above R¹The definitions are the same;

the dashed bonds indicate bonds to adjacent building blocks.

In one embodiment, the Y is₁、Y₂、Y₃、Y₄、Y₅And Y₆Absent, or each independently selected from the following groups:

R⁹、R¹⁰a ring may be formed.

For purposes of the present invention, an aromatic ring system contains 5 to 10 ring atoms in the ring system and a heteroaromatic ring system contains 1 to 10 carbon atoms and at least one heteroatom in the ring system, 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. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.

For the purposes of the present invention, the nonaromatic ring systems contain 1 to 10, preferably 1 to 3, carbon atoms in the ring system andincluding not only saturated but also partially unsaturated cyclic systems, which may be unsubstituted or substituted by radicals R₁Mono-or polysubstituted, the radical R₁May be identical or different on each occurrence and may also contain one or more heteroatoms, preferably Si, N, P, O, S and/or Ge, particularly preferably selected from Si, N, P, O and/or S. These may be, for example, cyclohexyl-like or piperidine-like systems, but also cyclooctadiene-like cyclic systems. The term also applies to fused non-aromatic ring systems.

In one embodiment, L1, L2, L3, L4, L5 and L6 are each independently selected from linear, branched and cyclic alkanes having 1-15 carbon atoms, aromatic, heteroaromatic or non-aromatic ring systems having 5-20 ring atoms.

In one embodiment, L1, L2, L3, L4, L5, and L6 are each independently selected from the group consisting of linear alkanes, branched alkanes, and cyclic alkanes comprising 1-15 carbon atoms.

In one embodiment, L1, L2, L3, L4, L5, and L6 are each independently selected from the group having the following structure:

wherein n1 is 1,2,3 or 4.

In one embodiment, at least one of L1, L2, L3, L4, L5, or L6 comprises an electron donating group, and/or at least one comprises an electron withdrawing group.

In one embodiment, the electron donating group is selected from the group consisting of:

in a preferred embodiment, the electron withdrawing group is selected from the group consisting of:

wherein r is 1,2 or 3;

X¹–X⁸is CR¹²Or N, and X¹–X⁸At least one of which is N;

Z₁-Z₃is a single bond, O, S or C (R)¹²)₂(ii) a Wherein R is¹²Comprises the following steps: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, or heteroaryl.

In a particularly preferred embodiment, Ar¹～Ar⁷Is phenyl. More preferably, the compounds according to the invention have one of the following formulae:

wherein the symbol definitions are the same as above.

In one embodiment, the nitrogen-containing heterocyclic compound has a general formula shown in chemical formula (8):

ring A, B is absent or each is independently selected from the group consisting of:

the term "small molecule" as defined herein refers to a compound other than a molecule of a polymer, oligomer, dendrimer, or blend. In particular, there is no repeat structure in small molecules. The small molecules have a molecular weight of 4000 g/mol or less, preferably 3000 g/mol or less, most preferably 2000 g/mol or less.

Polymers, i.e., polymers, include homopolymers (homo polymers), copolymers (copolymers), and block copolymers. In addition, the term "polymer" as used herein also includes Dendrimers (dendromers), and reference is made to the synthesis and use of Dendrimers, Wiley-VCH Verlag GmbH & Co.KGaA,2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.

Conjugated polymer is a polymer whose main chain backbone is mainly sp of C atoms²Hybrid track formation, notable examples are: polyacetylene and poly (phenylene vinylene), wherein the C atom of the main chain can be substituted by other non-C atoms, and when sp is present on the main chain²Hybridization is interrupted by some natural defect and is still considered a conjugated polymer. In the present invention, the conjugated polymer may include arylamines (aryl amines), aryl phosphines (aryl phosphines) and other heterocyclic aromatic hydrocarbons (heterocyclic aromatics), organic metal complexes (organometallic complexes) in the main chain.

Depending on the substitution pattern, the nitrogen-containing heterocyclic compound according to chemical formula (1) to chemical formula (8) may have various functions including, but not limited to, a hole transporting function, an electron transporting function, a light emitting function, an exciton blocking function, and the like. In particular, those compounds are described as being particularly suitable for those functions via the substituents L1 to L6. The substituents L1 to L6 influence the electronic properties of the units of the formulae (1) to (8).

In a preferred embodiment, the nitrogen-containing heterocyclic compounds according to the present invention are at least partially deuterated, preferably 10% H is deuterated, more preferably 20% H is deuterated, even more preferably 30% H is deuterated, and most preferably 40% H is deuterated.

The compounds according to the invention can be used as functional materials in electronic devices, in particular in OLED devices. Organic functional materials can be classified into Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), emitters (Emitter), Host materials (Host), and organic dyes. In a preferred embodiment, the compounds according to the invention can be used as host materials, or electron-transport materials, or hole-transport materials.

In a preferred embodiment, the nitrogen-containing heterocyclic compound according to the present invention may be used as a phosphorescent host material or a co-host material.

As a phosphorescent host material, it must have an appropriate triplet energy level, i.e., T₁. In certain embodiments, the compounds according to the invention, T thereof₁More preferably, it is not less than 2.2eV, still more preferably not less than 2.4eV, still more preferably not less than 2.6eV, still more preferably not less than 2.65eV, particularly preferably not less than 2.7 eV.

Generally, the triplet energy level T1 of a nitrogen-containing heterocyclic compound depends on the substructure with the largest conjugated system in the compound. Generally, T1 decreases with increasing conjugation system. In certain preferred embodiments, the partial structure of formula (1), as shown in formula (1a), has the largest conjugated system.

In certain embodiments, formula (1a) has no more than 36, preferably no more than 30, more preferably no more than 26, and most preferably no more than 20 ring atoms when the substituents are removed.

In certain preferred embodiments, T is of formula (1a)₁More preferably, it is not less than 2.3eV, still more preferably not less than 2.4eV, still more preferably not less than 2.5eV, still more preferably not less than 2.6eV, particularly preferably not less than 2.7 eV.

Good thermal stability is desired as a phosphorescent host material. Generally, the nitrogen-containing heterocyclic compounds according to the present invention have a glass transition temperature Tg of 100 deg.C or higher, in a preferred embodiment 120 deg.C or higher, in a more preferred embodiment 140 deg.C or higher, in a more preferred embodiment 160 deg.C or higher, and in a most preferred embodiment 180 deg.C or higher.

In certain preferred embodiments, the nitrogen-containing heterocyclic compounds according to the invention ((HOMO- (HOMO-1)). gtoreq.0.2 eV, preferably ≥ 0.25eV, more preferably ≥ 0.3eV, even more preferably ≥ 0.35eV, very preferably ≥ 0.4eV, most preferably ≥ 0.45 eV.

In further preferred embodiments, the nitrogen-containing heterocyclic compounds according to the invention have a (. di ((LUMO +1) -LUMO) > 0.15eV or more, preferably 0.20eV or more, more preferably 0.25eV or more, still more preferably 0.30eV or more, most preferably 0.35eV or more.

In some embodiments, the nitrogen-containing heterocyclic compound according to the present invention has a light-emitting function with a light-emitting wavelength of 300 to 1000nm, preferably 350 to 900nm, and more preferably 400 to 800 nm. Luminescence as used herein refers to photoluminescence or electroluminescence.

In another preferred embodiment, the nitrogen-containing heterocyclic compound according to the present invention can be used as a fluorescent host material.

Examples of the nitrogen-containing heterocyclic compounds according to the formulae (1) to (8) are listed below, but the structures are not limited to those which may be substituted at all possible points of substitution

The invention also relates to a nitrogen-containing heterocyclic polymer, and the repeating unit of the nitrogen-containing heterocyclic polymer comprises the structure of the nitrogen-containing heterocyclic compound.

In certain embodiments, the nitrogen-containing heterocyclic polymer is a non-conjugated polymer, wherein the structural unit of formula (I) is in a side chain. In another preferred embodiment, the nitrogen-containing heterocyclic polymer is a conjugated polymer.

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

In a preferred embodiment, the glass transition temperature (Tg) of the nitrogen-containing heterocyclic polymer according to the present invention is 100 ℃ or higher, preferably 120 ℃ or higher, more preferably 140 ℃ or higher, still more preferably 160 ℃ or higher, and most preferably 180 ℃ or higher.

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

In a preferred embodiment, the nitrogen-containing heterocyclic polymer according to the present invention preferably has a weight average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The invention also relates to a nitrogen-containing heterocyclic mixture, which comprises the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer and at least another organic functional material. The organic functional material comprises a hole (also called hole) injection or transmission material (HIM/HTM), a Hole Blocking Material (HBM), an electron injection or transmission material (EIM/ETM), an Electron Blocking Material (EBM), an organic Host material (Host), a singlet state light emitter (fluorescent light emitter), a triplet state light emitter (phosphorescent light emitter), an organic thermal excitation delay fluorescent material (TADF material) and especially a light-emitting organic metal complex. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain embodiments, the nitrogen-containing heterocyclic mixture comprises at least one nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the present invention and a fluorescent light emitter. The nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the present invention can be used as a fluorescent host material, wherein the fluorescent light-emitting substance is present in an amount of 10 wt% or less, preferably 9 wt% or less, more preferably 8 wt% or less, particularly preferably 7 wt% or less, and most preferably 5 wt% or less.

In a particularly preferred embodiment, the nitrogen-containing heterocyclic mixture comprises at least one nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the invention and a phosphorescent emitter. The nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer according to the present invention can be used as a phosphorescent host material, wherein the phosphorescent emitter is 25 wt% or less, preferably 20 wt% or less, and more preferably 15 wt% or less.

In a further preferred embodiment, the nitrogen-containing heterocyclic mixture comprises at least one nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the invention, a phosphorescent emitter and a further host material (triplet host material). In such embodiments, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer according to the present invention may be used as an auxiliary light emitting material in a weight ratio of 1:2 to 2:1 with respect to the phosphorescent emitter. In another preferred embodiment, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer according to the present invention forms an exciplex with another host material, and the exciplex has an energy level higher than that of the phosphorescent emitter.

In another preferred embodiment, the nitrogen-containing heterocyclic mixture comprises at least one nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the present invention and a TADF material. The nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer according to the present invention can be used as a host material of a TADF luminescent material, wherein the weight percentage of the TADF material is less than or equal to 15 wt%, preferably less than or equal to 10 wt%, and more preferably less than or equal to 8 wt%.

In a very preferred embodiment, the nitrogen-containing heterocyclic mixture comprises one nitrogen-containing heterocyclic compound according to the invention and another host material (triplet host material). The nitrogen-containing heterocyclic compound according to the present invention may be used as the second main body in an amount of 30 to 70% by weight, preferably 40 to 60% by weight.

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

1. Triplet Host material (Triplet Host):

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

m is a metal; (Y)³-Y⁴) Is a bidentate ligand, Y³And Y⁴Independently selected from C, N, O, P, and S; l is an ancillary ligand; q is an integer having a value from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complexes useful as triplet hosts are of the form:

q is an integer having a value from 1 up to the maximum coordination number of the metal;

in one embodiment, M may be selected from Ir and Pt.

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

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

R₂-R₇has the same meaning as R²，X⁹Is selected from CR₂R₃Or NR₂Y is selected from CR₂R₃Or NR₂Or O or S. R²，r1，X¹-X⁸，Ar¹～Ar³The meaning of (A) is as described above.

Examples of suitable triplet host materials are listed in the following table but are not limited to:

2. phosphorescent light-emitting material

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

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

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

Examples of 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, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

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

where M is a metal selected from the transition metals or the lanthanides or actinides, particularly preferably Ir, Pt, Au;

Ar₁each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)₂Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)₁And Ar₂Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0,1,2 or 3, preferably 2 or 3; q2 may be 0,1,2 or 3, preferably 1 or 0.

Examples of materials and their use for some triplet emitters can be found in WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, Baldo, Thompson et al. Nature 403, (2000), 750-and 753, US 2010099852A 2010099852, US 2010099852A 2010099852, Adachi. Appl. Phyt. Lett.78(2001), 1622-and 1624, J.Kido et al. Appl. Phys. Lett.65(1994), U.Kido.Phyt. 364, Chedo.657, US 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 3655, US 2010099852, US 2010099852, US 2010099852, WO 2012007088a1, WO2012007087a1, WO 2012007086a1, US 2008027220a1, WO 2011157339a1, CN 102282150a, WO 2009118087a1, WO 2013107487a1, WO 2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO 2014007565a1, WO 2014038456a1, WO 2014024131a1, WO 2014008982A1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

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

3. TADF material

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

TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in 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. appl.phys.lett, 101,2012,093306, Adachi, chem.comm.comm, 48,2012,11392, Adachi, et. nature. natronics, 6,2012,253, Adachi, et. nature,492,2012,234, Adachi, am.j.am, Adachi, et. adochi, et. nature, adochi, et. phytol.73, adochi, et. phyton.8, Adachi, adachi.73, et. phytol.73, Adachi, et. phyton.73, et. phytol.35, Adachi, et. phytol.8, Adachi, adachi.t.t.t.

Some examples of suitable TADF phosphors are listed in the following table:

it is an object of the present invention to provide a material solution for evaporation type OLEDs.

In certain embodiments, the nitrogen-containing heterocyclic compounds according to the present invention have a molecular weight of 1100g/mol or less, preferably 1000g/mol or less, very preferably 950g/mol or less, more preferably 900g/mol or less, and most preferably 800g/mol or less.

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

In certain embodiments, the nitrogen-containing heterocyclic compounds according to the present invention have a molecular weight of 700g/mol or more, preferably 900g/mol or more, very preferably 900g/mol or more, more preferably 1000g/mol or more, and most preferably 1100g/mol or more.

In other embodiments, the nitrogen-containing heterocyclic compounds according to the present invention have a solubility in toluene of 10mg/ml or more, preferably 15mg/ml or more, and most preferably 20mg/ml or more at 25 ℃.

The invention further relates to a nitrogen-containing heterocyclic composition or ink comprising an organic compound or polymer according to the invention and at least one organic solvent.

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

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

In another preferred embodiment, the viscosity of the ink according to the invention is in the range of about 1cps to about 100cps at the operating temperature or 25 ℃; preferably in the range of 1cps to 50 cps; more preferably in the range of 1.5cps to 20 cps; preferably in the range of 4.0cps to 20 cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of the functional material in the ink. The inks according to the invention comprising the organometallic complexes or polymers described facilitate the adjustment of the printing inks to the appropriate range according to the printing process used. Generally, the composition according to the present invention comprises the functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, still more preferably ranging from 0.5% to 10% by weight, and most preferably ranging from 1% to 5% by weight.

In some embodiments, the ink according to the invention, the at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents, in particular aliphatic chain/ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

Examples of solvents suitable for the present invention include aromatic or heteroaromatic solvents such as p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisophenyl, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, 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, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylacrylene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-methylphenidate, N-methylphenidate, 4-dimethoxyphenyl-4- (1, 2-propylphenyl) benzophenone, 1, 2-dimethoxybenzyl-2-dimethoxyphenyl-4- (1-propenyl) benzene, 2-dimethoxyphenyl) benzophenone, 2-dimethoxybenzyl-2-ethyl-2-phenoxyacetone, 2-dimethoxybenzyl-2-isopropyl-methyl-1, 2-isopropyl-2-methyl-2-methyl-phenyl-methyl-phenyl-methyl-benzene, 1, 2-methyl-ethyl-methyl-ethyl-methyl-2-ethyl-methyl-ethyl-methyl-2-ethyl-benzene, 2-ethyl-methyl-ethyl-benzene, 2-ethyl-methyl-ethyl-methyl-ethyl-benzene, 2-ethyl-methyl-butyl-ethyl-benzene, 1, 2-ethyl-methyl-ethyl-benzene, 2-ethyl-methyl-ethyl-benzene, 2-ethyl-methyl-ethyl-benzene, 2-butyl-methyl-ethyl-benzene, 2-ethyl-benzene, 2-ethyl-benzene, phenyl-benzene, phenyl-ethyl.

Further, according to the ink of the present invention, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, phorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

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

In a preferred embodiment, the nitrogen-containing heterocyclic composition according to the present invention is a solution.

In another preferred embodiment, the nitrogen-containing heterocyclic composition according to the present invention is a suspension.

The nitrogen-containing heterocyclic composition of the embodiment of the present invention may contain the organic compound according to the present invention or a mixture thereof in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably 0.25 to 5% by weight.

The invention also relates to the use of said nitrogen-containing heterocyclic composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferably by a printing or coating preparation process.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Ink jet printing, jet printing and gravure printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., see the Handbook of Print Media, techniques and Production Methods, published by Helmut Kipphan, ISBN3-540 and 67326-1.

Based on the above-mentioned nitrogen-containing heterocyclic compound, the present invention also provides a use of the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer as described above, namely, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer is applied to an Organic electronic device, which can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (fet), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic Plasmon Emitting Diode), and the like, and particularly preferred are Organic electroluminescent devices such as OLED, OLEEC, and an Organic light Emitting field effect transistor. In the embodiment of the present invention, the organic compound is preferably used for a light emitting layer of an electroluminescent device.

The invention further relates to an organic electronic device comprising at least one nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer as described above. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer 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 (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer comprising one of the organic compounds or polymers, or one of the organic compounds or polymers and a phosphorescent emitter, or one of the organic compounds or polymers and a host material, or one of the organic compounds or polymers, a phosphorescent emitter and a host material.

In the above-described electroluminescent device, in particular an OLED, comprising a substrate, an anode, at least one light-emitting layer, a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

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

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

In a preferred embodiment, the light-emitting device according to the invention has a light-emitting layer which is prepared from a composition according to the invention.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

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

The invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

Example 1

The synthetic route of compound (1) is as follows:

a1000 ml bottle was charged with intermediate A (35g, 57mmol), reduced iron powder (13.3g, 239.4mmol), ammonium chloride (14.2g, 239.4mmol) and 10ml of concentrated HCl and 800ml of MeOH/THF/H₂And mixing the solvent O, heating to 70 ℃ in an air environment for reaction, and tracking the reaction by TLC. After the reaction was complete, the reaction was cooled to room temperature, the solvent was removed by rotary evaporation, extracted with dichloromethane and washed with weak base water to neutrality, and silica gel was passed through DCM to give 29.0g of pure product in about 81% yield. Ms (asap) ═ 579.1.

Compound B (4g, 6.88mmol), palladium acetate (0.2g, 0.75mmol), sodium tert-butoxide (3.56g,34.9mmol) and 200mL of toluene were added to a 500mL three-necked flask under anhydrous and oxygen-free conditions. Tri-tert-butylphosphine (3ml, 0.15mmol) was added. The reaction was heated to 105 ℃ under nitrogen atmosphere overnight. After the reaction was complete, cooled to room temperature, quenched with water, extracted with dichloromethane and washed with water to neutrality, and purified by eluent column chromatography to give 1.2g of crude product with a yield of about 41.7%. Ms (asap) ═ 419.4.

Example 2

In this example, the final product compound (2) was synthesized in a similar manner to the compound (1) in example 1, using the same reaction temperature and reaction time, and the final reaction yield was 51.4%. Ms (asap) ═ 519.5

Example 3

In this example, the final product compound (3) was synthesized in a similar manner to the compound (1) in example 1, using the same reaction temperature and reaction time, and the final reaction yield was 38.5%. Ms (asap) ═ 651.4

Example 4

In this example, the final product compound (4) was synthesized in a similar manner to the compound (1) in example 1, using the same reaction temperature and reaction time, and the final reaction yield was 28.8%. Ms (asap) ═ 749.6

Example 5

The synthetic route of compound 5 is shown in the following figure:

in this example, the synthesis of the final product compound (5) was similar to the synthesis of compound (1) in example 1, except that the intermediate was changed from A to C, and the reaction temperature and reaction time were the same. Ms (asap) ═ 535.4

Example 6

In this example, the final product compound (6) was synthesized in a similar manner to the compound (1) in example 1, using the same reaction temperature and reaction time, and the final reaction yield was 38.4%. Ms (asap) ═ 751.6.

Example 7

In this example, the final product compound (7) was synthesized in a similar manner to the compound (1) in example 1, using the same reaction temperature and reaction time, and the final reaction yield was 55.2%. Ms (asap) ═ 747.4.

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration equation, S₁，T₁And resonance factor f (S)₁) Can be used directly.

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

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

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results are shown in table one:

watch 1

Wherein the resonance factor f (S)₁) The N atoms are fixed on the benzene unit on the triarylamine, so that the rotation and vibration of the benzene unit are well limited, and the migration probability from the S1 energy level to the S0 is increased.

Compared with the extended phosphorescent host material, the conventional and classical phosphorescent host material mCP is marked by Ref1, and the structure of the mCP is similar to that of the host material:

preparing an OLED device:

having ITO/NPD (35 nm)/compounds (1) to (5): 10% (ftp)₂The preparation steps of the OLED device of Ir (acac) (40nm)/TPBi (65nm)/LiF (1nm)/Al (150 nm)/cathode are as follows:

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

b. HTL (35nm), EML (40nm), ETL (35nm) under high vacuum (1 × 10)^-6Mbar, mbar) by thermal evaporation;

c. cathode-LiF/Al (1nm/150nm) in high vacuum (1 × 10)^-6Millibar) hot evaporation;

d. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. It was examined that the luminous efficiency and lifetime of OLED1 (corresponding to compound (1)) were 5.3 times higher than those of OLED Ref1 (corresponding to raw material (Ref1)), OLED3 (corresponding to compound (3)) were 2.5 times higher than those of OLED Ref1, and the lifetime was 4.4 times, and in particular, the maximum external quantum efficiency of OLED3 reached 20% or more. All devices are red light emitting devices. Therefore, the OLED device prepared by the organic mixture has greatly improved luminous efficiency and service life, and the external quantum efficiency is obviously improved.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (15)

1. A nitrogen-containing heterocyclic compound characterized by having a structure represented by the following formula (1):

   

   wherein:

   Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶and Ar⁷Each independently selected from: an aromatic, heteroaromatic or non-aromatic ring system having 5 to 20 ring atoms, optionally further substituted by one or more R¹Substituted by groups;

   l1, L2, L3, L4, L5 and/or L6 are absent or each independently selected from: linear, branched and cyclic alkanes having 1 to 15 carbon atoms, aromatic, heteroaromatic or nonaromatic ring systems having 5 to 20 ring atoms;

   Y₁、Y₂、Y₃、Y₄、Y₅and/or Y₆Is absent, or is each independently selected from a single bond, a di-bridge or a tri-bridge group, and Y is₁、Y₂、Y₃、Y₄、Y₅And/or Y₆Is connected with three adjacent groups by single bond or double bond;

   when said Y is₁、Y₂、Y₃、Y₄、Y₅Or Y₆When it is a single bond or a di-bridging group, with said Y₁、Y₂、Y₃、Y₄、Y₅Or Y₆The linked L is absent;

   when there are more than one R¹When a plurality of R¹Same or different, said R¹Selected from H, F, Cl, Br, I, D, CN, NO₂、CF₃、B(OR²)₂、Si(R²)₃Straight-chain alkane, branched-chain alkane, cycloalkane, alkane ether or alkane thioether containing 1-10 carbon atoms;

   R²selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atomsA radical group, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy group having 3 to 20C atoms, a thioalkoxy group having 3 to 20C atoms, a silyl group, a substituted keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A group, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms; and R is²The radicals in (a) may be bonded to one another and/or to the ring to which they are attached to form a mono-or polycyclic, aliphatic or aromatic ring system;

   R³is as defined for R²；

   n is 0,1 or 2;

   m is 0,1 or 2.
2. The nitrogen-containing heterocyclic compound according to claim 1, wherein Ar is¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently selected from aromatic or heteroaromatic rings having 5 to 20 ring atoms.
3. The nitrogen-containing heterocyclic compound according to claims 1 to 2, wherein Ar is the same as or different from Ar¹、Ar²、Ar³、Ar⁴、Ar⁵、Ar⁶And Ar⁷Each independently is a group comprising at least one of the following structures:

   

   wherein:

   when X is plural in the same group, each X is independently selected fromN or CR₅；

   When there are plural Y's in the same group, each Y is independently CR₆R₇，SiR₆R₇，NR₆Or, C (═ O), S, or O; r₅、R₆、R₇Is as defined for R²。
4. The nitrogen-containing heterocyclic compound according to claims 1 to 3, characterized by having a structural unit represented by any one of the structural formulae (2) to (7):

   
5. the nitrogen-containing heterocyclic compound according to any one of claims 1 to 4, characterized in that the di-or tri-bridging group is selected from the following groups:

   

   

   wherein:

   R⁹、R¹⁰and R¹¹Definitions of and R²The definitions of (A) are the same;

   the dashed bonds indicate bonds to adjacent building blocks.
6. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 5, wherein at least one of L1, L2, L3, L4, L5, or L6 contains an electron-donating group, and/or at least one contains an electron-withdrawing group.
7. The nitrogen-containing heterocyclic compound according to claim 6, characterized in that the electron-donating group is selected from the group consisting of:

   
8. the nitrogen-containing heterocyclic compound according to claim 6, characterized in that the electron-withdrawing group is selected from the group consisting of:

   

   

   wherein r is 1,2 or 3;

   X¹–X⁸is CR¹²Or N, and X¹–X⁸At least one of which is N;

   Z₁、Z₂、Z₃is a single bond, O, S or C (R)¹²)₂(ii) a Wherein R is¹²Is hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, or heteroaryl.
9. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 8, characterized by having a general formula represented by formula (8):

   

   ring a and/or ring B are absent or each independently selected from the following groups:

   
10. the nitrogen-containing heterocyclic compound according to any one of claims 1 to 9, characterized in that ((HOMO-1)) > 0.2 eV) of the nitrogen-containing heterocyclic compound.
11. A nitrogen-containing heterocyclic polymer characterized in that a repeating unit of the nitrogen-containing heterocyclic polymer comprises the structure of the nitrogen-containing heterocyclic compound according to any one of claims 1 to 10.
12. A nitrogen-containing heterocyclic compound comprising the nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or the nitrogen-containing heterocyclic polymer according to claim 11, and at least one organic functional material selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, and a host material.
13. A nitrogen-containing heterocyclic composition comprising a nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or a nitrogen-containing heterocyclic polymer according to claim 11, and at least one organic solvent.
14. An organic electronic device comprising at least one nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or a nitrogen-containing heterocyclic polymer according to claim 11.
15. The organic electronic device according to claim 14, wherein the organic electronic device is an electroluminescent device, and the nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or the nitrogen-containing heterocyclic polymer according to claim 11 is used as a material for a light-emitting layer.