WO2019128599A1 - Nitrogen-containing heterocyclic compound, high polymer, mixture, composition, and use thereof - Google Patents

Abstract

The present invention relates to a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition, and a use thereof. The nitrogen-containing heterocyclic compound has a structure represented by chemical formula (1). The nitrogen-containing heterocyclic compound, the high polymer, the mixture, and the composition are simple to synthesize, and fix benzene rings of two triarylamines using an N atom, thereby increasing the rigidity of material molecules, improving the stability of the material, and prolonging the life of light-emitting devices prepared therefrom. Further, the above nitrogen-containing heterocyclic compound, the high polymer, the mixture, and the composition can be used as a red and green phosphorescent host material, and when blended with a suitable guest material, can improve the luminous efficiency and life of electroluminescent devices, thereby providing a solution for manufacturing a light-emitting device having low manufacturing costs, high efficiency, a long service life, and low roll-off.

Description

Nitrogen-containing heterocyclic compounds, polymers, mixtures, compositions and uses thereof

The present application claims priority to Chinese Patent Application No. 200911451351.4, entitled "A Nitrogen-Containing Heterocyclic Compound and Its Use", on December 27, 2017, the entire contents of which are incorporated herein by reference. In the application.

Technical field

This invention relates to the field of electroluminescent materials, and more particularly to nitrogen-containing heterocyclic compounds, polymers, mixtures, compositions and uses thereof.

Background technique

Organic semiconductor materials have diverse versatility in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and illumination.

So far, fluorescent and phosphorescent-based luminescent material systems have been developed. Organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescence quantum efficiency is limited to 25% under electrical excitation. Because the branch ratio of the singlet excited state and the triplet excited state of the exciton is 1:3. In contrast, organic light-emitting diodes using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency. However, the stability of phosphorescent OLEDs needs to be improved. The stability of the OLED, in addition to the illuminant itself, the main material is the key.

For red and green phosphorescent devices, the phosphorescent host material of the light-emitting layer is mainly some carbazole organic compounds. Due to the shortcomings such as insufficient structural rigidity, the stability of such host materials is limited, resulting in low lifetime of the device. In order to further improve the stability of the host material, Kyoto University of Japan (WO2012118164) fixed the three benzene rings of triarylamine by two ether chains to obtain better device results, but the lone pair of oxygen atoms still cause material stability. not enough. In 2011, a material company of Japan (JP5724588B2) synthesized a benzene ring on one of the triarylamines with a single bond, but the conjugate range was still small, so that the rigidity was small, and the benzene ring on the other triarylamine was still It can be rotated so that the stability of the host material is still insufficient. In JP2016219487A, JP2012234873A, the rotation of three benzenes on a triarylamine is defined by introducing a six-membered ring or a hetero atom, but the lifetime of the OLED device prepared as a phosphorescent host material still needs to be further improved.

Therefore, new materials have yet to be improved and developed for overcoming the problem of insufficient stability and rigidity of current phosphorescent host materials.

Summary of the invention

In view of the above deficiencies of the prior art, the present invention aims to provide a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition and use thereof, and aims to solve the problem that the existing phosphorescent host luminescent material has insufficient stability and rigidity. problem.

The technical solution of the present invention is as follows:

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

among them:

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from the group consisting of aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 ring atoms, said aromatic a family, heteroaromatic or non-aromatic ring system optionally further substituted with one or more R ¹ groups;

L1, L2, L3, L4, L5 and/or L6 are absent or are each independently selected from the group consisting of a linear alkane group having 1 to 15 carbon atoms, a branched alkane group and a cycloalkane group having 5 to 20 An aromatic, heteroaromatic or non-aromatic ring system of a ring atom;

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and/or Y ₆ are absent, or are each independently selected from a single bond, a second bridge or a _triple bridged group, and said Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y _{6 are} bonded to the adjacent three groups by a single bond or a double bond;

When the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ is a single bond or a second bridge group, it is connected to the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ L does not exist;

When a plurality of R ¹ are present, the plurality of R ^{1 are the} same or different, and the R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, -NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , linear alkane group, branched alkane group, cycloalkane group, alkane ether group or alkane sulfide group having 1 to 10 carbon atoms;

R ^{2 is} selected from the group consisting of 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 of 3 to 20 C atoms, an alkoxy group having 3 to 20 C atoms, a thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted 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, 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 , CF ₃ group, Cl, Br, F, crosslinkable group, substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, aromatic having 5 to 40 ring atoms An oxy or heteroaryloxy group; and the groups in R ² may be bonded to each other and/or to a ring to which the group is attached to form a monocyclic or polycyclic aliphatic or aromatic ring system;

R ³ is defined as R ² ;

n is 0, 1 or 2;

m is 0, 1, or 2.

A nitrogen-containing heterocyclic high polymer, wherein the repeating unit of the nitrogen-containing heterocyclic high polymer comprises the structure of the above nitrogen-containing heterocyclic compound.

A nitrogen-containing heterocyclic mixture comprising the above nitrogen-containing heterocyclic compound or the above nitrogen-containing heterocyclic high polymer, and at least one organic functional material, which may be selected from a hole injecting material, a hole transporting Materials, electron transport materials, electron injecting materials, electron blocking materials, hole blocking materials, illuminants or host materials.

A nitrogen-containing heterocyclic composition comprising the above nitrogen-containing heterocyclic compound or the above nitrogen-containing heterocyclic high polymer, and at least one organic solvent.

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

The above nitrogen-containing heterocyclic compound, high polymer, mixture, and composition are simple to synthesize, and the benzene rings of two triarylamines are fixed by N atoms, thereby facilitating the rigidity of the material molecules and improving the stability of the material, thereby preparing a light-emitting device. Extend device life. Further, the above nitrogen-containing heterocyclic compound, high polymer, mixture, and composition can be used as a red, green, and phosphorescent host material, and by blending with a suitable guest material, the luminous efficiency and life of the electroluminescent device can be improved. A solution for a light-emitting device that is low in manufacturing cost, high in efficiency, long in life, and low in roll-off.

Detailed ways

The present invention provides a nitrogen-containing heterocyclic compound, a high polymer, a mixture, a composition, and a use thereof, and the present invention will be further described in detail below in order to clarify and clarify the objects, aspects, and effects of the present invention. It is 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, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.

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

In the present invention, the "number of ring atoms" means a structural compound (for example, a monocyclic compound, a fused ring compound, a crosslinking compound, a carbocyclic compound, or a heterocyclic compound) obtained by synthesizing a ring bond, which constitutes the ring itself. The number of atoms in an atom. When the ring is substituted by a substituent, the atom contained in the substituent is not included in the ring-forming atom. The "number of ring atoms" described below is also 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 levels ET1, HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

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

The triplet level ET1 of organic materials can be measured by low temperature time-resolved luminescence spectroscopy or by quantum simulation calculations (eg by Time-dependent DFT), such as by the commercial software Gaussian 03W (Gaussian Inc.), a specific simulation method. See WO2011141110 or as described below in the examples.

It should be noted that the absolute values of HOMO, LUMO, ET1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/LUMO. value. Therefore, reasonable and meaningful comparisons 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 ET1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is 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 present invention provides a nitrogen-containing heterocyclic compound represented by the chemical formula (1):

among them:

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from the group consisting of aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 ring atoms, said aromatic a family, heteroaromatic or non-aromatic ring system optionally further substituted with one or more R ¹ groups;

L1, L2, L3, L4, L5 and/or L6 are absent or are each independently selected from the group consisting of linear alkanes, branched alkanes and cycloalkanes having from 1 to 15 carbon atoms, having from 5 to 20 ring atoms An aromatic, heteroaromatic or non-aromatic ring system;

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and/or Y ₆ are absent, or are each independently selected from a single bond, a second bridge or a _triple bridged group, and said Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y _{6 are} bonded to the adjacent three groups by a single bond or a double bond;

When the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ is a single bond or a second bridge group, it is connected to the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ L does not exist;

When a plurality of R ¹ are present, the plurality of R ^{1 are the} same or different, and the R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si (R ² ) ₃ , a linear alkane, a branched alkane, a cycloalkane, an alkane ether or an alkane sulfide having 1 to 10 carbon atoms;

R ^{2 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 of 3 to 20 C atoms, an alkoxy group having 3 to 20 C atoms, a thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted 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, and a cyano group ( -CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(= O)-H), isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, an aryloxy group or a heteroaryloxy group having 5 to 40 ring atoms; And the groups in R ² may be bonded to each other and/or to the ring to which the group is attached to form a monocyclic or polycyclic aliphatic or aromatic group. Ring system

R ³ is defined as R ² ;

n is 0, 1 or 2;

m is 0, 1, or 2.

In one embodiment, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from the group consisting of an aromatic ring or a heteroaromatic ring having 5 to 20 ring atoms. The aromatic or heteroaromatic ring is optionally further substituted with one or more R ¹ groups.

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

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

Specifically, examples of the fused heterocyclic aromatic group are: benzofuran, benzothiophene, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran , thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-diazepine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone And its derivatives.

In one embodiment, according to the compound of the present invention, the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently a group comprising at least one of the following structures:

among them:

When X has more than one in the same group, each X is independently selected from N or CR ₅ ;

When Y has more than one in the same group, each Y is independently CR ₆ R ₇ , SiR ₆ R ₇ , NR ₆ or, C(=O), S, or O;

R ₅ , R ₆ and R _{7 have} the same meanings as R ² .

In one embodiment, the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently a group comprising at least one structure in which H on the ring can be optionally Replace:

In one embodiment, the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from the group consisting of:

In one embodiment, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ are the same or different each time they are a single bond or a two bridge or a triple bridge.

In one embodiment, the second or triple bridging group is selected from the group consisting of:

among them:

The definitions of R ⁹ , R ¹⁰ and R ¹¹ are the same as defined above for R ¹ ;

A dashed key indicates a key that is bonded to an adjacent structural unit.

In one embodiment, the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ are absent or are each independently selected from the group consisting of:

R ⁹ and R ¹⁰ may form a ring.

For the purposes of the present invention, an aromatic ring system contains 5 to 10 ring atoms in the ring system, and the heteroaromatic ring system contains 1 to 10 carbon atoms and at least one hetero atom in the ring system, provided that the carbon atom and the hetero atom are The total number is at least 4. The heteroatoms are preferably selected from the group consisting of Si, N, P, O, S and/or Ge, particularly preferably selected from the group consisting of 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 multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units (<10%). Non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.

For the purposes of the present invention, non-aromatic ring systems contain from 1 to 10, preferably from 1 to 3, carbon atoms in the ring system, and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or grouped R _{1 is} mono- or polysubstituted, the groups R ₁ may be the same or different in each occurrence, and may also contain one or more heteroatoms, preferably Si, N, P, O, S and/or Ge, in particular It is preferably selected from the group consisting of Si, N, P, O and/or S. These may, for example, be cyclohexyl- or piperidine-like systems or ring-like octadiene ring 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 the group consisting of linear alkanes, branched alkanes and cycloalkanes having from 1 to 15 carbon atoms, having aroma of from 5 to 20 ring atoms. Family, heteroaromatic or non-aromatic ring system.

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

In an embodiment, L1, L2, L3, L4, L5 and L6 are each independently selected from the group consisting of:

Where n1 is 1, 2, 3 or 4.

In one embodiment, at least one of the L1, L2, L3, L4, L5 or L6 contains an electron donating group, and/or at least one contains 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:

Where r is 1, 2 or 3;

X ¹ -X ⁸ is CR ¹² or N, and at least one of X ¹ -X ⁸ is N;

Z ₁ -Z ₃ is a single bond, O, S or C(R ¹² ) ₂ ; wherein R ¹² is: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl Or heteroaryl.

In a particularly preferred embodiment, Ar ¹ to Ar ⁷ are phenyl groups. More preferably, the compound according to the invention has one of the following formulas:

The symbol definition is the same as the above definition.

In one embodiment, the nitrogen-containing heterocyclic compound has the formula of the formula (8):

Rings A, B are absent or are each independently selected from the group consisting of:

The term "small molecule" as defined in this application refers to a compound other than the molecule of a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤ 4000 g/mol, preferably ≤ 3000 g/mol, preferably ≤ 2000 g/mol.

The polymer, that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. In addition, in the present invention, the high polymer also includes a dendrimer. For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

The conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp ² hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene). The C atom on the chain can also be substituted by other non-C atoms, and is still considered a conjugated polymer when the sp ² hybrid on the backbone is interrupted by some natural defects. Further, in the present invention, the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

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

In a preferred embodiment, the nitrogen-containing heterocyclic compound according to the present invention is at least partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, preferably 30% of H is deuterated, and preferably 40% of 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 injecting materials (EIM), electron blocking materials (EBM), and hole blocking materials (HBM). , Emitter, Host and Organic Dyes. In a preferred embodiment, the compound according to the invention may be used as a host material, or an electron transport material, or a hole transport material.

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

As a phosphorescent host material, there must be an appropriate triplet level, T ₁ . In certain embodiments, according to the compounds of the invention, T ₁ ≥ 2.2 eV, preferably ≥ 2.4 eV, more preferably ≥ 2.6 eV, still more preferably ≥ 2.65 eV, and most preferably ≥ 2.7 eV.

Generally, the triplet level T1 of the nitrogen-containing heterocyclic compound depends on the substructure of the compound having the largest conjugated system. Generally, T1 decreases as the conjugated system increases. In certain preferred embodiments, in the chemical formula (1), the substructure shown by the formula (1a) has the largest conjugated system.

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

In certain preferred embodiments, formula (1a) has T ₁ ≥ 2.3 eV, preferably ≥ 2.4 eV, more preferably ≥ 2.5 eV, still more preferably ≥ 2.6 eV, and most preferably ≥ 2.7 eV.

It is desirable to have good thermal stability as a phosphorescent host material. In general, the nitrogen-containing heterocyclic compound according to the present invention has a glass transition temperature Tg ≥ 100 ° C. In a preferred embodiment, Tg ≥ 120 ° C, in a more preferred embodiment, Tg ≥ 140 ° C, in a In a more preferred embodiment, Tg ≥ 160 ° C, and in a most preferred embodiment, Tg ≥ 180 ° C.

In certain preferred embodiments, the nitrogen-containing heterocyclic compound according to the present invention ((HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, more preferably It is ≥0.35 eV, very good ≥0.4 eV, preferably ≥0.45 eV.

In still other preferred embodiments, the nitrogen-containing heterocyclic compound according to the present invention (((LUMO+1)-LUMO) ≥ 0.15 eV, preferably ≥ 0.20 eV, more preferably ≥ 0.25 eV, more preferably It is ≥0.30 eV, preferably ≥0.35 eV.

In certain embodiments, the nitrogen-containing heterocyclic compound according to the present invention has a light-emitting function with an emission wavelength of from 300 to 1000 nm, preferably from 350 to 900 nm, more preferably from 400 to 800 nm. The luminescence referred to herein means 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 compound according to the chemical formula (1) to the chemical formula (8) are listed below, but are not limited thereto, and these structures may be substituted at all possible substitution points.

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

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

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

In a preferred embodiment, the nitrogen-containing heterocyclic high polymer according to the present invention has a glass transition temperature (Tg) ≥ 100 ° C, preferably ≥ 120 ° C, more preferably ≥ 140 ° C, still more preferably ≥ 160 ° C. The optimum is ≥180 °C.

In a preferred embodiment, the molecular weight distribution (PDI) of the nitrogen-containing heterocyclic high polymer according to the present invention preferably ranges from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, more It is preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the nitrogen-containing heterocyclic high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably 10 10,000 to 400,000, more preferably 150,000 to 300,000, and most preferably 200,000 to 250,000.

The invention further relates to a nitrogen-containing heterocyclic mixture comprising, for example, one of the above nitrogen-containing heterocyclic compounds or a nitrogen-containing heterocyclic polymer, and at least one other organic functional material. The organic functional materials include holes (also called holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), and electron blocking materials (EBM). ), organic host material (Host), singlet illuminant (fluorescent illuminant), heavy illuminant (phosphorescent illuminant), organic thermal excitation delayed fluorescent material (TADF material), especially luminescent organic metal complex. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated by reference. The organic functional material may be a small molecule and a 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 illuminant. Here, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic high polymer according to the present invention may be used as a fluorescent host material, wherein the fluorescent illuminant has a weight percentage of ≤ 10% by weight, preferably ≤ 9% by weight, more preferably ≤ 8% by weight. %, particularly preferably ≤ 7 wt%, preferably ≤ 5 wt%.

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. Here, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic high polymer according to the present invention may be used as a phosphorescent host material, wherein the phosphorescent emitter has a weight percentage of ≤25 wt%, preferably ≤20 wt%, more preferably ≤15 wt%. %.

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 invention, a phosphorescent emitter and another host material (Triple state material). In such an embodiment, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic polymer according to the present invention may be used as an auxiliary luminescent material in a weight ratio to phosphorescent emitter of from 1:2 to 2:1. In another preferred embodiment, the nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the present invention forms an exciplex with another host material, said exciplex The energy level is higher than the phosphorescent emitter.

In another preferred embodiment, the nitrogen-containing heterocyclic mixture comprises one less nitrogen-containing heterocyclic compound or nitrogen-containing heterocyclic polymer according to the present invention, and a TADF material. Here, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic high polymer according to the present invention may be used as a host material of the TADF luminescent material, wherein the weight percentage of the TADF material is ≤ 15% by weight, preferably ≤ 10% by weight, more preferably It is ≤ 8wt%.

In a highly preferred embodiment, the nitrogen-containing heterocyclic mixture comprises a nitrogen-containing heterocyclic compound according to the present invention, and another host material (trimeric host material). The nitrogen-containing heterocyclic compound according to the present invention may be used as the second host, and may have a weight percentage of 30% to 70%, preferably 40% to 60%.

The subject material, phosphorescent material and TADF material are described in some detail below (but are not limited thereto).

1. Triplet Host Material (Triplet Host):

The example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy level is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant. Examples of metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P, and S; L is an ancillary ligand; q is an integer The value is from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-toothed ligand in which a metal is coordinated with O and N atoms. q is an integer whose value ranges from 1 to the maximum coordination number of the metal;

In one embodiment, M is optional for Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazine, anthraquinone, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, Quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopypyridine, benzothienopyridine, thienopyridine, benzoselenophene Pyridine and selenophene benzopyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or Hong heterocyclic group, and at least one of the following groups coupled together directly or through another, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein, each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.

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

R ₂ -R ₇ have the same meaning as R ² , X ^{9 is} selected from CR ₂ R ₃ or NR ₂ , and Y is selected from CR ₂ R ₃ or NR ₂ or O or S. R ² , r1, X ¹ -X ⁸ and Ar ¹ to Ar ³ have the same meanings as described above.

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

2, phosphorescent materials

Phosphorescent emitters are also referred to as triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

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

Preferentially, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

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

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

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

Ar ₁ may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Connection; Ar ₂ may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar ₁ and Ar ₂ are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: 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 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000) ), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94 , 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1 , WO 20130 94620A1, WO 2013174471A1, WO 2014031977 A1, WO 2014112450 A1, WO 2014007565 A1, WO 2014038456 A1, WO 2014024131 A1, WO 2014008982 A1, WO 2014023377 A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

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

3. TADF materials

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE _st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, and secondarily 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, the TADF has a better fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), 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. Mater., 25, 2013, 3319, Adachi, et. .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, hereby incorporated by reference to The entire contents are incorporated herein by reference.

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

It is an object of the present invention to provide a material solution for an evaporated OLED.

In certain embodiments, the nitrogen-containing heterocyclic compound according to the invention has a molecular weight of ≤1100 g/mol, preferably ≤1000 g/mol, very preferably ≤950 g/mol, more preferably ≤900 g/mol, most preferably ≤800 g/mol.

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

In certain embodiments, the nitrogen-containing heterocyclic compound according to the invention has a molecular weight of ≥ 700 g/mol, preferably ≥ 900 g/mol, very preferably ≥ 900 g/mol, more preferably ≥ 1000 g/mol, most preferably ≥ 1100 g/mol.

In other embodiments, the nitrogen-containing heterocyclic compound according to the invention has a solubility in toluene of > 10 mg/ml, preferably > 15 mg/ml, most preferably > 20 mg/ml at 25 °C.

The invention still 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.

The viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.

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

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

The viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink. The ink containing the metal organic complex or polymer according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used. In general, the composition according to the invention comprises a functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight, even more preferably. It is in the range of 0.5% to 10% by weight, preferably in the range of 1% to 5% by weight.

In some embodiments, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention. Solvent, or aromatic ether solvent.

Examples of solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, two Hexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene , diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropane Pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetrahydronaphthalene Ketone, 2-tetralone, 2-(phenyl epoxy) tetralone 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methyl Acetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2 - anthrone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene, butyl Oxybenzene, benzylbutylbenzene, 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-ethylbenethyl ether, 1,2,4-trimethoxybenzene, 4 -(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans -p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl Ether, pentyl ether c hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; Ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, oleic acid Alkyl esters and the like.

Further, according to the ink of the present invention, the at least one solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene 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, 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, tetrahydronaphthalene , decalin, hydrazine 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 in the embodiment of the present invention may comprise 0.01 to 20% by weight of the organic compound or a mixture thereof according to the present invention, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably It is 0.25 to 5 wt% of an organic compound or a mixture thereof.

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

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are inkjet printing, jet printing and gravure printing. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN3-540-67326-1.

Based on the above nitrogen-containing heterocyclic compound, the present invention also provides the use of the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic high polymer as described above, that is, the nitrogen-containing heterocyclic compound or the nitrogen-containing heterocyclic high polymer Applied to organic electronic devices, the organic electronic device may 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), organic Luminescent field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field Effect tube. In the embodiment of the invention, the organic compound is preferably used for the light-emitting layer of the electroluminescent device.

The invention further relates to an organic electronic device comprising at least one of a nitrogen-containing heterocyclic compound or a nitrogen-containing heterocyclic polymer as described above. Typically, such an organic electronic device comprises at least one cathode, an anode and a functional layer 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 may 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, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.

In some particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer comprising one of the organic compounds or polymers, or an organic compound Or a high polymer and a phosphorescent emitter, or comprising one of said organic compounds or polymers and a host material, or comprising one of said organic compounds or polymers, a phosphorescent emitter and A host material.

In the above electroluminescent device, particularly the OLED, a substrate, an anode, at least one luminescent layer, and a cathode are included.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can 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 a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or 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 the anode material 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 can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material 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, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further 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, the entire contents of each of which are hereby incorporated by reference.

In a preferred embodiment, in the light-emitting device according to the invention, the light-emitting layer is prepared by the composition according to the invention.

The light-emitting device according to the present invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The invention further relates to the use of an organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.

The invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Example 1

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

Intermediate A (35 g, 57 mmol), reduced iron powder (13.3 g, 239.4 mmol), ammonium chloride (14.2 g, 239.4 mmol) and 10 ml of concentrated hydrochloric acid and 800 ml of MeOH/THF/H _{2 were} added to a 1000 ml bottle. O mixed solvent, heated to 70 ° C in an air environment, TLC tracking reaction. After the reaction was completed, it was cooled to room temperature, and the solvent in the reaction mixture was evaporated to dryness, and extracted with methylene chloride and washed to neutral with a weak base of water, and then purified by silica gel to give 29.0 g of pure product in a yield of about 81%. MS (ASAP) = 579.1.

Compound B (4 g, 6.88 mmol) and palladium acetate (0.2 g, 0.75 mmol) and sodium tert-butoxide (3.56 g, 34.9 mmol) were added to a 500 ml three-necked flask under anhydrous and anhydrous atmosphere. Tri-tert-butylphosphine (3 ml, 0.15 mmol) was added. In a nitrogen atmosphere, the temperature was raised to 105 ° C and heated overnight. After the reaction was completed, it was cooled to room temperature, quenched with water, extracted with methylene chloride and washed with water to neutral, and purified by eluant column chromatography to give crude product (1.2 g). MS (ASAP) = 419.4.

Example 2

In the present embodiment, the final product compound (2) was similar to the synthesis procedure of the compound (1) in Example 1, and the reaction temperature and the reaction time used in the reaction were the same, and the final one-step reaction yield was 51.4%. MS (ASAP) = 519.5

Example 3

In the present embodiment, the final product compound (3) was similar to the synthesis procedure of the compound (1) in Example 1, and the reaction temperature and the reaction time used in the reaction were the same, and the final one-step reaction yield was 38.5%. MS (ASAP) = 651.4

Example 4

In the present embodiment, the final product compound (4) was similar to the synthesis procedure of the compound (1) in Example 1, and the reaction temperature and the reaction time used in the reaction were the same, and the final one-step reaction yield was 28.8%. MS (ASAP) = 749.6

Example 5

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

In the present embodiment, the final product compound (5) is similar to the synthesis step of the compound (1) in Example 1, except that the intermediate is replaced with A to the intermediate C, and the reaction temperature and reaction used in the reaction. The time is the same. MS (ASAP) = 535.4

Example 6

In the present embodiment, the final product compound (6) was similar to the synthesis procedure of the compound (1) in Example 1, and the reaction temperature and the reaction time used in the reaction were the same, and the final one-step reaction yield was 38.4%. MS (ASAP) = 751.6.

Example 7

In the present embodiment, the final product compound (7) was similar to the synthesis procedure of the compound (1) in Example 1, and the reaction temperature and the reaction time used in the reaction were the same, and the final one-step 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 TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S ₁ , T ₁ and the resonance factor f(S ₁ ) are used directly.

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

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

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

Table I

Among them, the resonance factor f(S ₁ ) is between 0.0024 and 0.3288, which can improve the fluorescence quantum luminescence efficiency of the material, and the ΔHOMO value is greater than 0.50 eV. It has good stability and is fixed on the triarylamine by N atom. The benzene unit, which is a good restriction of the rotation and vibration of the benzene unit, increases the probability of migration from the S1 level to the S0.

A comparison with the above-mentioned phosphorescent host material is a commonly used and classical phosphorescent host material mCP, labeled with Ref 1 and having a structure similar to that of the host material:

Preparation of OLED devices:

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

a, cleaning of the conductive glass substrate: when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;

b, HTL (35 nm), EML (40 nm), ETL (35 nm): hot evaporation in high vacuum (1 × 10 ^-6 mbar, mbar);

c, cathode: LiF / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. It has been tested that the luminous efficiency and lifetime of OLED1 (corresponding to compound (1)) are 5.3 times that of OLED Ref1 (corresponding to raw material (Ref1)), and the luminous efficiency of OLED3 (corresponding to compound (3)) is 2.5 times that of OLED Ref1. The lifetime is 4.4 times, especially the maximum external quantum efficiency of OLED 3 is more than 20%. All devices are red light emitting devices. It can be seen that the OLED device prepared by using the organic mixture of the invention has greatly improved luminous efficiency and lifetime, and the external quantum efficiency is also significantly improved.

It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims (15)

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

   

   among them:

   Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from the group consisting of aromatic, heteroaromatic or non-aromatic ring systems having 5 to 20 ring atoms, said aromatic a family, heteroaromatic or non-aromatic ring system optionally further substituted with one or more R ¹ groups;

   L1, L2, L3, L4, L5 and/or L6 are absent or are each independently selected from the group consisting of linear alkanes, branched alkanes and cycloalkanes having from 1 to 15 carbon atoms, having from 5 to 20 ring atoms An aromatic, heteroaromatic or non-aromatic ring system;

   Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and/or Y ₆ are absent, or are each independently selected from a single bond, a second bridge or a _triple bridged group, and said Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and/or Y _{6 are} bonded to the adjacent three groups by a single bond or a double bond;

   When the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ is a single bond or a second bridge group, it is connected to the Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ or Y ₆ L does not exist;

   When a plurality of R ¹ are present, a plurality of R ^{1 are the} same or different, and R ^{1 is} selected from the group consisting of H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si (R ² ) ₃ , a linear alkane, a branched alkane, a cycloalkane, an alkane ether or an alkane sulfide having 1 to 10 carbon atoms;

   R ^{2 is} selected from the group consisting of 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 of 3 to 20 C atoms, an alkoxy group having 3 to 20 C atoms, a thioalkoxy group having 3 to 20 C atoms, a silyl group, a substituted 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, 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 , CF ₃ group, Cl, Br, F, crosslinkable group, substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, aromatic having 5 to 40 ring atoms An oxy or heteroaryloxy group; and the groups in R ² may be bonded to each other and/or to a ring to which the group is attached to form a monocyclic or polycyclic aliphatic or aromatic ring system;

   R ³ is defined as R ² ;

   n is 0, 1 or 2;

   m is 0, 1, or 2.
2. The nitrogen-containing heterocyclic compound according to claim 1, wherein the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are each independently selected from 5 to 20 rings. An aromatic or heteroaromatic ring of an atom.
3. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 2, wherein each of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ independently comprises at least one of the following Structure of the group:

   

   among them:

   When X has more than one in the same group, each X is independently selected from N or CR ₅ ;

   When Y is plural in the same group, each Y is independently CR ₆ R ₇ , SiR ₆ R ₇ , NR ₆ or, C(=O), S, or O; R ₅ , R ₆ , R ₇ The definition is the same as R ² .
4. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 3, which has a structural unit represented by any one of the chemical formulas (2) to (7):

   
5. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 4, wherein the di- or tri-bridged group is selected from the group consisting of:

   

   

   among them:

   R ⁹ , R ¹⁰ and R ¹¹ are the same as defined for R ² ;

   A dashed key indicates a key that is bonded to an adjacent structural unit.
6. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 5, wherein at least one of the 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, wherein the electron-donating group is selected from the group consisting of:

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

   

   

   Where r is 1, 2 or 3;

   X ¹ -X ⁸ is CR ¹² or N, and at least one of X ¹ -X ⁸ is N;

   Z ₁ , Z ₂ , Z ₃ are a single bond, O, S or C(R ¹² ) ₂ ; wherein R ¹² is 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, which has the formula represented by the chemical formula (8):

   

   Ring A and/or Ring B are absent or are each independently selected from the group consisting of:

   
10. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 9, which is ((HOMO-(HOMO-1)) ≥ 0.2 eV).
11. A nitrogen-containing heterocyclic high polymer characterized in that the repeating unit of the nitrogen-containing heterocyclic high polymer comprises the structure of the nitrogen-containing heterocyclic compound according to any one of claims 1 to 10.
12. A nitrogen-containing heterocyclic mixture, 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 The functional material may be selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant or a host material.
13. A nitrogen-containing heterocyclic composition, 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 solvent.
14. An organic electronic device comprising at least one nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or the nitrogen-containing heterocyclic high polymer according to claim 11.
15. The organic electronic device according to claim 14, wherein the organic electronic device is an electroluminescent device, the nitrogen-containing heterocyclic compound according to any one of claims 1 to 10 or the method of claim 11. The nitrogen-containing heterocyclic polymer described above is used as a material for the light-emitting layer.