WO2020151500A1 - Organic electroluminescent compound, electroluminescent material and organic electroluminescent device - Google Patents

Abstract

Disclosed herein are an organic electroluminescent compound, an electroluminescent material and an organic electroluminescent component. The organic electroluminescent compound has the structure of formula (1). The organic electroluminescent compound disclosed herein can be a fluorescent material exhibiting good properties. The organic electroluminescent device made of the fluorescent material disclosed herein exhibits advantages, such as low driving voltage, high luminescent efficiency, long service life, and highly pure optical chromatography.

Description

Organic electroluminescent compound, luminescent material and organic electroluminescent device Technical field

The present disclosure relates to an organic electroluminescent compound, a light emitting material containing the organic electroluminescent compound, and an organic electroluminescent device containing the organic electroluminescent compound.

Background technique

Since the Kodak company CWTang et al. reported for the first time in 1987 that a double-layer light-emitting device with Alq ₃ as a light-emitting material was prepared by a vacuum evaporation method, organic electroluminescent devices have received great attention. After more than 30 years of development, the introduction of organic electroluminescence in flat panel displays and lighting has entered the initial stage of industrialization.

Organic electroluminescence devices generally consist of an anode, a metal cathode and an organic layer sandwiched between them. The organic layer mainly includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The basic mechanism of organic electroluminescent devices involves the injection, transport, and recombination of charges, and the formation of excitons to emit light. When an external voltage is applied to the organic electroluminescence device, electrons and holes are injected from the cathode and anode, respectively, electrons will be injected from the cathode to the lowest unoccupied molecular orbital, and holes will be injected from the anode to the highest occupied molecular orbital. When electrons and holes recombine in the light-emitting layer, excitons are formed and then emit light. When the light-emitting molecule absorbs energy to an excited state, according to the statistical rules of electron spin, singlet excitons and triplet excitons are generated at a ratio of 25%:75%. Since the decay of the triplet excitons is spin forbidden, the internal quantum efficiency of the fluorescent electroluminescent device is only 25%. However, in phosphorescent materials containing heavy metal elements, there is a strong spin-orbit coupling in the molecule, which promotes the intersystem crossing between the singlet state and the triplet state, thereby obtaining both the singlet state and the triplet state. The internal quantum efficiency of phosphorescent electroluminescent devices can reach 100%.

In recent years, Professor Chibaya Adachi and his colleagues have developed a new type of fluorescent organic light-emitting device that combines a thermally activated delayed fluorescence mechanism. Through the reverse intersystem crossing mechanism, the spin-forbidden triplet excitons are converted into The singlet state obtains 100% internal quantum efficiency. Therefore, high-efficiency technologies for phosphorescence and delayed fluorescence electroluminescence devices have received extensive attention. However, phosphorescent and delayed fluorescence electroluminescent devices have short life and poor color purity compared with fluorescent electroluminescent devices. Especially in blue phosphorescent and delayed fluorescence electroluminescent devices, they have short life, poor color purity and luminous efficiency. It is not enough and has not yet reached practicality. In addition, currently commercialized fluorescent light-emitting materials include DPVBi, DSA-ph, dinaphthalene anthracene and so on. Due to the poor thermal stability of the above-mentioned materials, long-term driving will cause the color purity to decrease, resulting in problems such as color difference when the panel is applied. Therefore, it is urgent to develop a batch of new materials that can meet the requirements in terms of color purity, efficiency and thermal stability.

Summary of the invention

The problem to be solved by the invention

Based on the above reasons, the purpose of the present disclosure is to solve the problems of the prior art and provide an organic electroluminescent device with thermal stability, high luminous efficiency, high brightness, and long life.

Solutions to the problem

The present disclosure provides an organic electroluminescent compound, which is represented by the following formula (1):

In the formula (1),

M means C(R ¹ ) ₂ or

The dotted line represents the bond from M;

Z is the same or different every time it appears, which means C, CR ¹ or N;

A represents a substituted or unsubstituted condensed aromatic ring unit having 2 to 5 rings. Ar ¹ and Ar ² are the same or different each time they have 5 to 30 aromatic ring atoms and may be substituted by one or more A R ¹ substituted aromatic or heteroaromatic ring system;

R ¹ is the same or different each time H, D, F, Cl, Br, I, CN, NO ₂ , NR ² , OR ² , SR ² , C(=O)R ² , P(=O ) R ² , Si(R ² ) ₃ , substituted or unsubstituted linear or branched alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cyclic with 3 to 20 carbon atoms Alkyl, alkenyl or alkynyl having 2 to 20 carbon atoms, or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R ² Ring system; wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R ² in each case, and wherein one or more non-adjacent CH ₂ groups may be R ² C=CR ^2. C≡C, Si(R ² ) ₃ , C=O, C=NR ² , P(=O)R ² , SO, SO ₂ , NR ² , O, S or CONR ² instead, and one of them or Multiple hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ;

Wherein, two adjacent R ¹ or two adjacent R ² optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, and the ring system may be composed of one or more R ^{2 is} substituted; and two or more R ¹ may be connected to each other and form a ring;

R ² is the same or different in each case and is selected from H, D, F, CN, aliphatic groups having 1 to 20 carbon atoms, aromatic or heteroaromatic groups having 5 to 30 aromatic ring atoms A ring system, or an aliphatic ring system with multiple rings, in which one or more hydrogen atoms can be substituted by D, F, or CN.

The organic electroluminescent compound according to the present disclosure, wherein A in the formula (1) has a structure selected from the group consisting of the following formulas:

Wherein R ₂ to R _{15 are} independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and groups having 3 to 30 carbon atoms. A group of substituted or unsubstituted heteroaromatic groups with three carbon atoms.

The organic electroluminescent compound according to the present disclosure is represented by any one of the following formulas (1-1) to (1-4):

Among them, Ar ¹ , Ar ² , M, Z, and A are the same as defined in formula (1).

The organic electroluminescent compound according to the present disclosure, wherein the compound represented by the formula (1) is selected from the following compounds:

The present disclosure also provides a luminescent material, which includes the organic electroluminescent compound according to the present disclosure.

The light-emitting material according to the present disclosure is a fluorescent light-emitting guest material.

The present disclosure also provides an organic electroluminescent device, which includes: a first electrode, a second electrode provided opposite to the first electrode, and sandwiched between the first electrode and the second electrode At least one organic layer,

The organic layer includes the organic electroluminescent compound according to the present disclosure.

The organic electroluminescent device according to the present disclosure, wherein the organic layer containing the organic electroluminescent compound is a light emitting layer.

Effect of invention

The spirobifluorene molecule has a non-planar space structure. Two fluorene monomers are bridged together with sp ³ hybridized carbon atoms as the center to obtain an orthogonal three-dimensional structure with excellent thermal stability and film-forming properties. More importantly, the steric hindrance between molecules is large, which can effectively reduce the output of unfavorable factors such as excimer and concentration quenching. Therefore, introducing it into molecules with electroluminescent properties is beneficial to improve Molecular stability, color purity and luminous efficiency, etc.

The beneficial effect of the present disclosure is that the luminescent material prepared by the present disclosure has a higher glass transition temperature, fluorescence quantum yield, and charge mobility, which can increase the efficiency and lifetime of the organic electroluminescent device and reduce the driving voltage and power consumption. The compound of formula (1) of the present disclosure, as a light-emitting material (doping compound) of an organic electroluminescent device, can stabilize the film state and has excellent heat resistance. By using the compound, organic electroluminescent devices with high efficiency, high brightness, long life, and low driving voltage can be prepared.

Description of the drawings

Figure 1 shows the ultraviolet absorption spectrum (UV-Vis) and room temperature fluorescence spectrum (PL) of the luminescent material compound 83 in OLED3 in the embodiment; the ultraviolet absorption spectrum and room temperature fluorescence spectrum in a dilute solution of dichloromethane (1×10 ^-5) mol/L).

Figure 2 shows the organic electroluminescence spectra of OLED2 and OLED3 in the embodiment.

Fig. 3 is a diagram showing the configuration of organic electroluminescent devices of Examples and Comparative Examples.

Description of reference signs

1 substrate

2 anode

3 hole injection layer

4 Hole Transport Layer I

5 Hole Transport Layer II

6 electron blocking layer

7 luminescent layer

8 hole blocking layer

9 electron transport layer

10 electron injection layer

11 cathode

detailed description

Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited by the following embodiments.

References to "one embodiment" or "embodiment" or "in another embodiment" or "in certain embodiments" or "in some embodiments of this application" throughout this specification mean that At least one embodiment includes specific reference elements, structures, or features related to the embodiment. Therefore, the phrases "in one embodiment" or "in an embodiment" or "in another embodiment" or "in certain embodiments" or "in part of this application" appearing in various places throughout the specification In the embodiments, "not all refer to the same embodiment. In addition, specific elements, structures, or features may be combined in one or more embodiments in any suitable manner.

Unless otherwise required in this application, throughout the specification and the following claims, the word "comprise" and its English variants such as "comprises" and "comprising" shall be interpreted as open-ended The inclusive meaning of "including but not limited to".

It should be understood that the singular article "一" (corresponding to English "a", "an" and "the") used in the description of this application and the appended claims includes plural objects unless the context clearly indicates otherwise Local regulations. It should also be understood that the term "or" is usually used in its meaning including "and/or", unless the context clearly specifies otherwise.

The organic electroluminescent compound of the present disclosure is represented by the following formula (1):

In the formula (1),

M means C(R ¹ ) ₂ or

The dotted line represents the bond from M;

Z is the same or different every time it appears, which means C, CR ¹ or N;

A represents a substituted or unsubstituted condensed aromatic ring unit having 2 to 5 rings. Ar ¹ and Ar ² are the same or different each time they have 5 to 30 aromatic ring atoms and may be substituted by one or more A R ¹ substituted aromatic or heteroaromatic ring system;

R ¹ is the same or different each time H, D, F, Cl, Br, I, CN, NO ₂ , NR ² , OR ² , SR ² , C(=O)R ² , P(=O ) R ² , Si(R ² ) ₃ , substituted or unsubstituted linear or branched alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cyclic with 3 to 20 carbon atoms Alkyl, alkenyl or alkynyl having 2 to 20 carbon atoms, or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R ² Ring system; wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R ² in each case, and wherein one or more non-adjacent CH ₂ groups may be R ² C=CR ^2. C≡C, Si(R ² ) ₃ , C=O, C=NR ² , P(=O)R ² , SO, SO ₂ , NR ² , O, S or CONR ² instead, and one of them or Multiple hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ;

Wherein, two adjacent R ¹ or two adjacent R ² optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, and the ring system may be composed of one or more R ^{2 is} substituted; and two or more R ¹ may be connected to each other and form a ring;

R ² is the same or different in each case and is selected from H, D, F, CN, aliphatic groups having 1 to 20 carbon atoms, aromatic or heteroaromatic groups having 5 to 30 aromatic ring atoms A ring system, or an aliphatic ring system with multiple rings, in which one or more hydrogen atoms can be substituted by D, F, or CN.

As an example of a condensed aromatic ring unit having 2 to 5 rings in the formula (1), specific examples include biphenyl, terphenyl, tetraphenyl, naphthalene, anthracene, acenaphthylene, fluorene, phenanthrene, indene , Pyrene, perylene, fluoranthene, benzanthracene, triphenylene, etc.

As the substituent on the fused aromatic ring unit, the following can be exemplified:

Deuterium atom,

Cyano,

Nitro,

Halogen atom, such as fluorine atom, chlorine atom, bromine atom or iodine atom;

An alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl Or n-hexyl;

An alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy or propoxy;

Alkenyl, such as vinyl or allyl;

Aryloxy, such as phenoxy or tolyloxy;

Arylalkoxy, such as benzyloxy or phenethoxy;

Aromatic hydrocarbon groups or condensed polycyclic aromatic groups, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylene, fluoranthene, benzene And [9,10] phenanthryl or spirobifluorenyl;

Aromatic heterocyclic groups, such as pyridyl, thienyl, furyl, pyrrolyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazole Group, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, azafluorenyl, diazafluorenyl, carboline, aza Spirobifluorenyl or diazaspirobifluorenyl;

Aryl vinyl groups, such as styryl or naphthalene vinyl groups; and

Acyl, for example acetyl or benzoyl.

The aromatic ring system represented by Ar ¹ and Ar ² can be exemplified by benzene, biphenyl, terphenyl, tetraphenyl, styrene, naphthalene, anthracene, acenaphthene, phenanthrene, fluorene, indene, pyrene, perylene, fluoranthene, benzene And [9,10] phenanthrene, snail difluorene and so on.

The heteroaromatic ring system represented by Ar ¹ and Ar ² can exemplify pyridine, bipyridine, terpyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, pyrazole, imidazole, triazole, oxazole, isooxazole Azole, thiazole, isothiazole, oxadiazole, thiadiazole, furan, thiophene, quinoline, isoquinoline, quinoxaline, quinazoline, naphthyridine, indole, isoindole, benzimidazole, benzo Triazole, benzofuran, benzothiophene, benzoxazole, benzoxadiazole, benzothiazole, benzothiadiazole, pyridopyrrole, pyridoimidazole, pyridotriazole, pteridine, acridine , Phenazine, phenanthroline, phenoxazine, phenothiazine, phenselazine, phenothrazine, phenphosphorazine, carbazole, carboline, dibenzofuran, dibenzothiophene, xanthene, etc.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms in R ¹ of the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n Decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, iso Myristyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecanyl, isoheptadecanyl, n-octadecyl, isooctadecyl Alkyl, n-nonadecyl, isonadecanyl, n-eicosyl, isoeicosyl, etc.

As the cyclic alkyl group having 3 to 20 carbon atoms in R ¹ of the formula (1), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo Decyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecanyl, cyclooctadecyl , Cyclononadecyl, cycloeicosyl, 1-adamantyl, 2-adamantyl, etc.

As the alkenyl or alkynyl group having 2 to 20 carbon atoms in R ¹ of the formula (1), vinyl, allyl, isopropenyl, 2-butenyl, 1-pentenyl, 2 -Hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, 1-octadecenyl, 1-nonadecanyl, 1-eicosenyl, 2 -Heptenyl, 2-methyl-2-hexenyl, 2-octenyl, 2-ethylhexenyl, 3-methyl-2-heptenyl, 2-nonenyl, 2-decenyl Alkenyl, 2-hexadecenyl, 2-octadecenyl; ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decyne Group, 1-undecynyl, 1-dodecynyl, 1-tridecynyl, 1-tetradecynyl, 1-pentadecynyl, 1-hexadecynyl, 1-hexadecynyl , 1-octadecynyl, 1-nonadecynyl, 1-eicosynyl and the like.

As an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms in R ¹ of formula (1), the same as the above-mentioned aromatic or heteroaromatic ring system represented by Ar ¹ and Ar ² can be exemplified example of.

As the substituent in R ¹ of the formula (1), the same examples as the substituent on the above-mentioned condensed aromatic ring unit can be illustrated.

As an aliphatic group having 1 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in R ² of formula (1), the same as those in the above R ¹ The same example.

As an aliphatic ring system having a polycyclic ring in R ² of the formula (1), an alicyclic epoxy compound and the like can be exemplified.

As the substituent in R ² of the formula (1), the same examples as the substituent in R ¹ described above can be illustrated.

Preferably, A in the formula (1) has a structure selected from the group consisting of the following formulas:

Wherein R ₂ to R _{15 are} independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and groups having 3 to 30 carbon atoms. A group of substituted or unsubstituted heteroaromatic groups with three carbon atoms.

As the alkyl group, the aryl group, and the heteroaromatic group here, the same examples as in the above-mentioned Ar ¹ , Ar ² , R ¹ , and R ² can be illustrated.

Preferably, the organic electroluminescent compound of the present disclosure is represented by any one of the following formulas (1-1) to (1-4):

Among them, Ar ¹ , Ar ² , M, Z, and A are the same as defined in formula (1).

Preferably, the organic electroluminescent compound of the present disclosure is selected from the following compounds, but the present disclosure is not limited to these compounds.

The purification of the organic electroluminescent compound of the present disclosure is performed by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization using a solvent, crystallization method, sublimation purification method, and the like. The identification of organic electroluminescent compounds is performed by mass spectrometry and elemental analysis.

<Luminescent Material>

The light-emitting material of the present disclosure includes the above-mentioned organic electroluminescent compound.

The luminescent material of the present disclosure can be used in organic electroluminescent devices, especially as a fluorescent light-emitting guest material of organic electroluminescent devices.

<Organic Electroluminescence Device>

The organic electroluminescence device of the present disclosure includes: a first electrode, a second electrode provided opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the organic layer contains the present Disclosed organic electroluminescent compound.

FIG. 3 is a diagram showing the configuration of the organic electroluminescent device of the present disclosure. As shown in FIG. 3, in the organic electroluminescent device of the present disclosure, for example, the anode 2, the hole injection layer 3, the hole transport layer I4, the hole transport layer II5, the electron blocking layer 6, the light emitting layer 7, the air The hole blocking layer 8, the electron transport layer 9, the electron injection layer 10 and the cathode 11 are arranged on the substrate 1 in this order.

The organic electroluminescent device of the present disclosure is not limited to such a structure, for example, in the multilayer structure, some organic layers may be omitted. For example, it can be the hole injection layer 3 between the anode 2 and the hole transport layer I4, the hole blocking layer 8 between the light-emitting layer 7 and the electron transport layer 9, and the electrons between the electron transport layer 9 and the cathode 11. The injection layer 10 is omitted, and the configuration of the anode 2, the hole transport layer I4, the light emitting layer 7, the electron transport layer 9 and the cathode 11 are sequentially arranged on the substrate 1.

The organic electroluminescent device according to the present disclosure can be manufactured by materials and methods known in the art, except that the above-mentioned organic layer contains the compound represented by the above-mentioned formula (1). In addition, in the case where the organic electroluminescence device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic electroluminescent device according to the present disclosure may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. At this time, it can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or their alloy is vapor-deposited on a substrate to form an anode, Then, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a substance that can be used as a cathode is vapor-deposited on the organic layer. However, the manufacturing method is not limited to this.

As an example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

As the anode of the organic electroluminescent device of the present disclosure, it may be composed of a known electrode material. For example, use electrode materials with large work functions, such as vanadium, chromium, copper, zinc, gold and other metals or their alloys; such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) and other metals Oxide; such as ZnO: Al or SNO ₂ : Sb and other metal and oxide combinations; poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene]( PEDOT), conductive polymers such as polypyrrole and polyaniline. Among these, ITO is preferable.

As the hole injection layer of the organic electroluminescence device of the present disclosure, a known material having hole injection properties can be used. Examples include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, and divalent groups with three or more triphenylamine structures in the molecule through single bonds or no heteroatoms Triphenylamine trimers and tetramers such as arylamine compounds with a group-linked structure, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

As the hole transport layers I and II of the organic electroluminescent device of the present disclosure, well-known materials having hole transport properties can be used. Examples include: compounds containing m-carbazolyl phenyl; such as N,N'-diphenyl-N,N'-bis(m-tolyl)benzidine (TPD), N,N'-diphenyl- N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N,N',N'-tetraphenylbenzidine and other benzidines Derivatives; 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9',9”-triphenyl Base-9H,9'H,9"H-3,3':6',3"-Tris-PCz, etc.. They can be formed into a film alone or mixed with other materials to form a film It can be used in the form of a single layer, and it can also be made into a laminated structure of layers formed by separate films, a laminated structure of layers formed by mixed films, or layers formed by separate films and mixed films The laminated structure of the resulting layer. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

In addition, in the hole injection layer or the hole transport layer, it is also possible to use a material obtained by P-doping tribromoaniline antimony hexachloride, axene derivatives, etc., for the materials commonly used in the layer, and its partial structure Polymer compounds having the structure of benzidine derivatives such as TPD.

As the electron blocking layer of the organic electroluminescent device of the present disclosure, it can be formed using a known compound having an electron blocking effect. For example, 3,3'-bis(N-carbazolyl)-1,1'-biphenyl (mCBP), 4,4',4"-tris(N-carbazolyl) triphenylamine ( TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), 2,2-bis(4- Carbazole derivatives such as carbazole-9-ylphenyl)adamantane (Ad-Cz); 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilane) (Yl)phenyl]-9H-fluorene represented by compounds having triphenylsilyl and triarylamine structures; monoamine compounds with high electron blocking properties, various triphenylamine dimers, and other compounds with electron blocking effects. They can be formed into a film individually, or they can be used in the form of a single layer formed by mixing with other materials, and can also be formed into a laminated structure of layers formed by separate films, or layers formed by mixing and forming films. The laminated structure of, or the laminated structure of the layer formed separately and the layer formed by mixing the film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

As the light-emitting layer of the organic electroluminescent device of the present disclosure, a light-emitting material containing the organic electroluminescent compound represented by formula (1) is preferably used. In addition, various metal complexes such as metal complexes of quinoline derivatives such as Alq ₃ , compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, Pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, etc.

The light-emitting layer may be composed of a host material and a dopant material. As the host material, for example, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, and the like can be used.

As the dopant material, a light-emitting material containing an organic electroluminescent compound represented by formula (1) is preferably used. The doping weight ratio of the organic electroluminescent compound of the present disclosure is preferably 0.1-50%, more preferably 0.5-20%, and particularly preferably 0.5-8%.

In addition to the organic electroluminescent compounds of the present disclosure, the dopant materials can also use pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrene, perylene and their derivatives, benzopyrene Pyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirocyclic bifluorene derivatives, etc. They can be formed into a film individually, or they can be used in the form of a single layer formed by mixing with other materials, and can also be formed into a laminated structure of layers formed by separate films, or layers formed by mixing and forming films. The laminated structure of, or the laminated structure of the layer formed by separate film formation and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

As the hole blocking layer of the organic electroluminescent device of the present disclosure, it can be formed using a known compound having hole blocking properties. For example, 2,4,6-tris(3-phenyl)-1,3,5-triazine (T2T), 1,3,5-tris(1-phenyl-1H-benzimidazole-2- Phenanthroline derivatives such as benzene (TPBi) and bath copper spirit (BCP), and quinolines such as aluminum (III) bis(2-methyl-8-hydroxyquinoline)-4-phenylphenolate (BAlq) Metal complexes of alcohol derivatives, and various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having hole blocking effects. They can be formed into a film alone, or they can be used in the form of a single layer formed by mixing with other materials, or they can be formed into a laminated structure of layers formed separately, or a layer formed by mixing. The laminated structure of each other, or the laminated structure of the layer formed by separate film formation, and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

The material having hole blocking properties described above can also be used for the formation of the electron transport layer described below. That is, by using the above-mentioned well-known material having hole blocking properties, it is possible to form a layer that serves as both a hole blocking layer and an electron transport layer.

As the electron transport layer of the organic electroluminescence device of the present disclosure, a known compound having electron transport properties is used. For example, metal complexes of quinoline derivatives headed by Alq ₃ and BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; bis(10 -Hydroxybenzo[H]quinoline)beryllium (Be(bq ₂ )); such as 2-[4-(9,10-dinaphthalene-2-anthracene-2-yl)phenyl]-1-phenyl- Benzimidazole derivatives such as 1H-benzimidazole (ZADN); thiadiazole derivatives; anthracene derivatives; carbodiimide derivatives; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives ; Silole derivatives and so on. They can be formed into a film alone, or they can be used in the form of a single layer formed by mixing with other materials, or they can be formed into a laminated structure of layers formed separately, or a layer formed by mixing. The laminated structure of each other, or the laminated structure of the layer formed by separate film formation, and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

As the electron injection layer of the organic electroluminescence device of the present disclosure, it can be formed using a material known per se. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolate; metal oxides such as alumina.

In the electron injection layer or the electron transport layer, as the material generally used in the layer, a material obtained by further N-doping metals such as cesium, triarylphosphine oxide derivatives, and the like can be used.

As the cathode of the organic electroluminescence device of the present disclosure, it is preferable to use an electrode material having a low work function such as aluminum and magnesium, or an alloy having a low work function such as magnesium silver alloy, magnesium indium alloy, and aluminum magnesium alloy as the electrode material.

As the substrate of the present disclosure, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In this disclosure, a glass substrate is selected.

Example

In the following examples, the production of the compound represented by the above formula (1) and the organic electroluminescence device containing the compound will be specifically described. However, the following embodiments are only used to illustrate the present disclosure, and the scope of the present disclosure is not limited thereto.

Preparation Example 1:

This preparation example is used to prepare compound 44, and its structural formula and synthetic route are shown in the figure below:

Synthesis of intermediate 44A

In a 250mL Schlenk bottle, add 10.19g (25.77mmol) of 4-bromo-9,9'-spirobisfluorene, 3.00g (15.00mmol) of aniline, 0.36g (1.6mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.93 g (3.22 mmol) of borate, 9.29 g (96.64 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was stirred at reflux for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 30 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether:dichloromethane=3:1 (V/V)), the solvent is evaporated, and after drying, 9.70 g of white solid is obtained, with a yield of 73.9%. MS(EI): m/z 407.541[M+]. Anal.calcd for C ₃₁ H ₂₁ N(%): C,91.37; H,5.19; N,3.44; found: C,91.26; H,5.27; N, 3.47.

Synthesis of compound 44

In a 250mL Schlenk bottle, add intermediate 44A 5.00g (12.27mmol), 9,10-dibromoanthracene 1.65g (4.91mmol), tris(dibenzylideneacetone)dipalladium 0.22g (0.25mmol), tert 0.14 g (0.49 mmol) of butylphosphine tetrafluoroborate, 2.36 g (24.54 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, reflux and stir for 12 hours, and the reaction is complete. Evaporate the solvent, dissolve the residue with 200 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane=2.5:1 (V/V)), the solvent is evaporated, and after drying, 3.20 g of white crystals are obtained, with a yield of 65.9%. MS(EI): m/z 988.47[M+]. Anal.calcd for C ₇₆ H ₄₈ N ₂ (%): C, 92.28; H, 4.89; N, 2.83; found: C, 92.15; H, 4.87; N ,2.98.

Preparation Example 2:

This preparation example is used to prepare compound 74, and its structural formula and synthetic route are shown in the figure below:

Synthesis of intermediate 74A

In a 250mL Schlenk bottle, add 7.04g (25.77mmol) of 9,9-dimethyl-2-bromofluorene, 3.00g (32.21mmol) of aniline, 0.36g (1.61mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.93 g (3.22 mmol) of borate, 9.29 g (96.64 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was stirred at reflux for 12 hours, and the reaction was completed. The solvent was evaporated, the residue was dissolved with 150 mL of dichloromethane and 100 mL of water, washed with water, and the organic layer was separated. The aqueous layer was extracted twice with 15 mL of dichloromethane. The organic layers were combined and the solvent was evaporated. The residue was separated by column chromatography. (The silica gel is 350 mesh, and the eluent is petroleum ether:dichloromethane=4:1 (V/V)), the solvent is evaporated, and after drying, 6.20 g of white crystals are obtained, with a yield of 67.44%. MS(EI): m/z 285.34[M+]. Anal.calcd for C ₂₁ H ₁₉ N(%): C,88.38; H,6.71; N,4.91; found: C,88.35; H,6.68; N, 4.97.

Synthesis of compound 74

In a 250mL Schlenk bottle, add intermediate 74A 5.00g (17.52mmol), 1,6-diisopropyl-3,8-dibromopyrene 3.11g (7.01mmol), tris(dibenzylideneacetone)dipalladium 0.32g (0.35mmol), 0.20g (0.70mmol) of tri-tert-butylphosphine tetrafluoroborate, 3.37g (35.04mmol) of sodium tert-butoxide, 150mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.60 g of white crystals are obtained, with a yield of 60.2%. MS(EI): m/z 852.68[M+]. Anal.calcd for C ₆₄ H ₅₆ N ₂ (%): C, 90.10; H, 6.62; N, 3.28; found: C, 90.24; H, 6.57; N , 3.19.

Preparation Example 3:

This preparation example is used to prepare compound 83, and its structural formula and synthetic route are shown in the following figure:

Synthesis of Intermediate 83A

In a 250mL Schlenk bottle, add 5.90g (14.93mmol) of 3-bromo-9,9'-spirobisfluorene, 2.00g (18.66mmol) of aniline, 0.21g (0.09mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.54 g (1.87 mmol) of borate, 5.38 g (56.0 mmol) of sodium tert-butoxide, 120 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 200 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, and the eluent is petroleum ether: dichloromethane = 2:1 (V/V)), the solvent is evaporated, and after drying, 6.40 g of white crystals are obtained with a yield of 81.3%. MS(EI): m/z 407.61[M+].Anal.calcd for C ₃₁ H ₂₁ N(%): C,91.37; H,5.19; N,3.44; found: C,91.31,H,5.23; N, 3.46.

Synthesis of compound 83

In a 250mL Schlenk bottle, add 2.00g (4.74mmol) of Intermediate 83A, 1.00g (2.06mmol) of 1,6-diisopropyl-3,8-dibromopyrene, and tris(dibenzylideneacetone)dipalladium 0.09g (0.1mmol), 0.06g (0.2mmol) of tri-tert-butylphosphine tetrafluoroborate, 0.99g (10.31mmol) of sodium tert-butoxide, 100mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 1.55 g of white crystals are obtained, and the yield is 66.76%. MS(EI): m/z 1096.75[M+]. Anal.calcd for C ₈₄ H ₆₀ N ₂ (%): C, 91.94; H, 5.51; N, 2.55; found: C, 91.86; H, 5.57; N ,2.57.

Preparation Example 4:

This preparation example is used to prepare compound 87, and its structural formula and synthetic route are shown in the following figure:

Synthesis of intermediate 87A

In a 250mL Schlenk bottle, add 4.68g (11.83mmol) of 3-bromo-9,9'-spirobisfluorene, 2.00g (14.79mmol) of 4-isopropylaniline, 0.17g (0.74mmol) of palladium acetate, and tertiary 0.43 g (1.48 mmol) of butyl phosphine tetrafluoroborate, 4.26 g (44.38 mmol) of sodium tert-butoxide, 120 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 2:1 (V/V)), the solvent is evaporated, and after drying, 5.65 g of white crystals are obtained with a yield of 85%. MS(EI): m/z 449.71[M+].Anal.calcd for C ₃₄ H ₂₇ N(%): C,90.83; H,6.05; N,3.12; found: C,90.73; H,6.13; N, 3.14.

Synthesis of compound 87

In a 250mL Schlenk bottle, add intermediate 87A 5.00g (11.12mmol), 1,6-diisopropyl-3,8-dibromopyrene 1.98g (4.45mmol), tris(dibenzylideneacetone)dipalladium 0.20g (0.22mmol), 0.13g (0.44mmol) of tri-tert-butylphosphine tetrafluoroborate, 2.14g (22.24mmol) of sodium tert-butoxide, 150mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.30 g of white crystals are obtained, with a yield of 62.8%. MS(EI): m/z 1180.54[M+]. Anal.calcd for C ₉₀ H ₇₂ N ₂ (%): C, 91.49; H, 6.14; N, 2.37; found: C, 91.34; H, 6.37; N , 2.29.

Preparation Example 5:

This preparation example is used to prepare compound 98, and its structural formula and synthetic route are shown in the figure below:

Synthesis of compound 98

In a 250mL Schlenk bottle, add 6.00g (21.02mmol) of intermediate 74A, 3.25g (8.41mmol) of 6,12-dibromide, 0.38g (0.42mmol) of tris(dibenzylideneacetone) dipalladium, and tert 0.24 g (0.84 mmol) of butyl phosphine tetrafluoroborate, 4.04 g (42.05 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.60 g of white crystals are obtained, with a yield of 60.2%. MS(EI): m/z 794.87[M+]. Anal.calcd for C ₆₀ H ₄₆ N ₂ (%): C,90.64; H,5.83; N,3.52; found: C,90.62; H,6.87; N ,2.51.

The following are application examples of the compounds of the present disclosure

Example

The hole injection layer 3, the hole transport layer I 4, the hole transport layer II 5, the electron blocking layer 6, the light emitting layer 7, the hole blocking layer 8, the electron transport layer 9, the electron injection layer 10, and the cathode 11 are sequentially formed On the transparent anode 2 previously formed on the glass substrate 1 to prepare an organic electroluminescent device as shown in FIG. 3.

Specifically, the glass substrate coated with a transparent conductive layer of ITO with a thickness of 100nm was ultrasonically processed in Decon 90 alkaline cleaning solution, rinsed in deionized water, rinsed in acetone and ethanol three times each, and baked in a clean environment To completely remove the water, clean with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam. The glass substrate with the ITO electrode is placed in the vacuum chamber and evacuated to 4×10 ^-5 to 2×10 ^-5 Pa.

Then, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexacyano-1,4,5,8,9,12- is evaporated on the above-mentioned glass substrate with ITO electrode at an evaporation rate of 0.2nm/s Hexaazatriphenylene (HAT-CN) is formed with a thickness of 10nm as the hole injection layer (HIL). On the hole injection layer, N, N'is deposited at an evaporation rate of 2.0nm/s -Diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) to form a layer with a thickness of 40nm as the hole transport layer I ( HTL I), and then on the hole transport layer I (HTL I), 9,9',9”-triphenyl-9H,9'H,9”H- is evaporated at an evaporation rate of 2.0nm/s 3,3':6',3”-tricarbazole (Tris-PCz) is formed with a thickness of 20nm as the hole transport layer II (HTL II). On the hole transport layer II, the thickness is 2.0nm/ s evaporation rate 3,3'-bis(N-carbazolyl)-1,1'-biphenyl (mCBP) is evaporated to form a layer with a film thickness of 15nm as the electron blocking layer (EBL). On the layer, the evaporation rate of 9-(4-(1-naphthyl)-10-(2-naphthyl)anthracene (NNPA) is 2.0nm/s and that of Preparation Examples 1, 2, 3, 4, 5 The vapor deposition rate of the compounds (compounds 44, 74, 83, 87, and 98) was 0.16nm/s. The vapor deposition rate was 0.16nm/s. Dual source co-evaporation was performed to form a layer with a thickness of 20nm as the light-emitting layer. Preparation Examples 1, 2, 3 The doping mass ratio of the compounds of, 4, and 5 (compounds 44, 74, 83, 87, and 98) is 8wt%. On the light-emitting layer, 2,4,6-three are evaporated at an evaporation rate of 2.0nm/s. (3-Phenyl)-1,3,5-triazine (T2T) is formed with a thickness of 10nm as the hole blocking layer (HBL). On the hole blocking layer, vapor deposition is performed at 2.0nm/s Rate deposition of 2-[4-(9,10-dinaphthalene-2-anthracene-2-yl)phenyl]-1-phenyl-1H-benzimidazole (ZADN) to form a layer with a thickness of 40nm as Electron transport layer (ETL). On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) is vapor-deposited at a vapor deposition rate of 0.2 nm/s to form a layer with a thickness of 2 nm as the electron injection layer. Finally, use Aluminum is vapor deposited at a vapor deposition rate of 3.0 nm/s or more to form a cathode with a film thickness of 100 nm.

Device performance test: The current-brightness-voltage characteristics of the device are completed by the Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode, and the electroluminescence spectrum is performed by the Photoresearch company PR655 spectrometer Measured, the external quantum efficiency of the device can be calculated by the method of Adv. Mater., 2003, 15, 1043-1048. The lifetime of the device refers to the time for the brightness to decay to 9,000 canter per square meter (90%) starting with 10,000 canter per square meter. All devices are packaged in a nitrogen environment.

The structures of the compounds involved in the examples are as follows:

The structure of the organic electroluminescent device (OLED1-5) prepared in the example and the film thickness of each layer are as follows:

OLED1:

ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:44(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED2:

ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:74(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED3:

ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:83(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED4:

ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:87(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED5:

ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:98(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

Comparative example

The preparation methods of Comparative Examples 1 and 2 are the same as the Examples, except that the fluorescent light-emitting compound is changed.

The device structure of Comparative Example 1 is as follows:

ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:DPAVBi(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

The device structure of Comparative Example 2 is as follows:

ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:C545T(20nm, 5wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

The performance data of the devices of the embodiment and the comparative example are shown in Table 1 below.

Table 1 Device performance data

It can be seen from Table 1 that compared with Comparative Examples 1 and 2, the luminous efficiency and device lifetime of the green and blue organic electroluminescent devices prepared with the fluorescent light-emitting materials of the present disclosure are significantly improved. In addition, the color purity of the blue organic electroluminescent device is obviously better than that of the organic electroluminescent device prepared by using the sky blue material DPAVBi in the prior art.

Industrial availability

The organic electroluminescent compound of the present disclosure has excellent luminous efficiency, excellent material color purity and lifetime characteristics. Therefore, organic electroluminescent devices with excellent service life can be prepared from the compound.

Claims (8)

1. An organic electroluminescent compound represented by the following formula (1):

   

   In the formula (1),

   M means C(R ¹ ) ₂ or

   

   The dotted line represents the bond from M;

   Z is the same or different every time it appears, which means C, CR ¹ or N;

   A represents a substituted or unsubstituted condensed aromatic ring unit having 2 to 5 rings. Ar ¹ and Ar ² are the same or different each time they have 5 to 30 aromatic ring atoms and may be substituted by one or more A R ¹ substituted aromatic or heteroaromatic ring system;

   R ¹ is the same or different each time H, D, F, Cl, Br, I, CN, NO ₂ , NR ² , OR ² , SR ² , C(=O)R ² , P(=O ) R ² , Si(R ² ) ₃ , substituted or unsubstituted linear or branched alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cyclic with 3 to 20 carbon atoms Alkyl, alkenyl or alkynyl having 2 to 20 carbon atoms, or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R ² Ring system; wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R ² in each case, and wherein one or more non-adjacent CH ₂ groups may be R ² C=CR ^2. C≡C, Si(R ² ) ₃ , C=O, C=NR ² , P(=O)R ² , SO, SO ₂ , NR ² , O, S or CONR ² instead, and one of them or Multiple hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ;

   Wherein, two adjacent R ¹ or two adjacent R ² optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, and the ring system may be composed of one or more R ^{2 is} substituted; and two or more R ¹ may be connected to each other and form a ring;

   R ² is the same or different in each case and is selected from H, D, F, CN, aliphatic groups having 1 to 20 carbon atoms, aromatic or heteroaromatic groups having 5 to 30 aromatic ring atoms A ring system, or an aliphatic ring system with multiple rings, in which one or more hydrogen atoms can be substituted by D, F, or CN.
2. The organic electroluminescent compound according to claim 1, wherein A in the formula (1) has a structure selected from the group consisting of the following formulas:

   

   Wherein R ₂ to R _{15 are} independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and groups having 3 to 30 carbon atoms. A group of substituted or unsubstituted heteroaromatic groups with three carbon atoms.
3. The organic electroluminescent compound according to claim 1 or 2, which is represented by any one of the following formulas (1-1) to (1-4):

   

   

   Among them, Ar ¹ , Ar ² , M, Z, and A are the same as defined in formula (1).
4. The organic electroluminescent compound according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is selected from the following compounds:

   

   

   

   
5. A luminescent material comprising the organic electroluminescent compound according to any one of claims 1 to 4.
6. The luminescent material of claim 5, which is a fluorescent luminescent guest material.
7. An organic electroluminescence device comprising: a first electrode, a second electrode provided opposite to the first electrode, and at least one organic electroluminescence device sandwiched between the first electrode and the second electrode. layer,

   Wherein the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 4.
8. The organic electroluminescent device according to claim 7, wherein the organic layer containing the organic electroluminescent compound is a light emitting layer.

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