阅读说明：本技术 化合物、其应用及包含其的有机电致发光器件 (Compound, application thereof and organic electroluminescent device comprising compound ) 是由 李之洋 黄鑫鑫 于 2019-09-29 设计创作，主要内容包括：本发明提供了一种化合物、其应用及包含其的有机电致发光器件。该化合物具有以下结构：X～1～X～(12)各自独立地为CR～3或CR～4,且至少一个为CR～4；R～3选自氢、C-1～C-(12)链状烷基、C-3～C-(12)环烷基、C-1～C-(12)烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基和取代或未取代的C-6～C-(30)芳基中的一种；R～4选自取代或未取代的C-6～C-(30)芳基氨基、取代或未取代的C-3～C-(30)杂芳基氨基、取代或未取代的C-3～C-(30)杂芳基中的一种；R～1和R～2各自独立地选自C-1～C-(12)链状烷基、C-3～C-(12)环烷基、取代或未取代的C-6～C-(30)芳基、取代或未取代的C-3～C-(30)杂芳基中的一种,R～1和R～2可以成环。以提高器件电流效率。(The invention provides a compound, application thereof and an organic electroluminescent device comprising the compound. The compound has the following structure: X 1 ～X 12 each independently is CR 3 Or CR 4 And at least one is CR 4 ；R 3 Selected from hydrogen, C 1 ～C 12 Chain alkyl, C 3 ～C 12 Cycloalkyl radical, C 1 ～C 12 Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino and substituted or unsubstituted C 6 ～C 30 One of aryl groups; r 4 Selected from substituted or unsubstituted C 6 ～C 30 Arylamino, substituted or unsubstituted C 3 ～C 30 Heteroarylamino, substituted or unsubstituted C 3 ～C 30 One of heteroaryl; r 1 And R 2 Each independently selected from C 1 ～C 12 Chain alkyl, C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 3 ～C 30 One of the heteroaryl groups, R 1 And R 2 A ring may be formed. To improve device current efficiency.)

1. A compound having the structure of formula (I):

wherein, X¹～X¹²Each independently is CR³Or CR⁴And at least one is CR⁴；

R³Selected from hydrogen, C₁～C₁₂Chain alkyl, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino and substituted or unsubstituted C₆～C₃₀Any one of aryl groups;

R⁴selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₃～C₃₀Any one of heteroaryl, said C₃～C₃₀Heteroaryl includes an electron-deficient group C₃～C₃₀Heteroaryl and electron donor C₃～C₃₀Heteroaryl, said substituted or unsubstituted C₃～C₃₀Electron deficient heteroaryl is an electron deficient group, said substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino group and said substituted or unsubstituted C₃～C₃₀An electron-donating heteroaryl group is an electron-donating group;

R¹and R²Each independently selected from C₁～C₁₂Chain alkyl、C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₃～C₃₀One of the heteroaryl groups, R¹R²Can form a ring;

when the above groups have substituents, the substituents are selected from halogen and C₁～C₁₂Chain alkyl group of (1), C₃～C₁₂Cycloalkyl of, C₂～C₁₀Alkenyl radical, C₁～C₆Alkoxy or thioalkoxy of C₆～C₃₀Monocyclic aromatic hydrocarbon or condensed-ring aromatic hydrocarbon group of C₃～C₃₀Or a combination of at least two of the monocyclic or fused ring heteroaromatic hydrocarbon groups of (a).

2. The compound of claim 1, wherein X is¹～X¹²In (2) the CR⁴The number of (A) is 1 or 2; preferably said X¹～X¹²Middle CR⁴The number of (2) is 1.

3. A compound according to claim 1 or 2, wherein the CR is⁴Is located at the X⁴、X⁶～X⁸Any one or more of the loci; preferably the CR⁴Is located at the X⁴、X⁶～X⁸Any one or two of the loci; more preferably, the CR⁴Is located at the X⁴、X⁶～X⁸Any one of the loci.

4. A compound according to any one of claims 1 to 3, wherein X is¹～X¹²At least one of which is the CR⁴And wherein R is⁴Selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Any one of heteroarylamino groups.

5. According to any one of claims 1 to 3The compound of (1), wherein X is¹～X¹²At least one of which is the CR⁴And wherein R is⁴Is substituted or unsubstituted C₃～C₃₀Electron deficient heteroaryl.

6. The compound of claim 1, wherein X is¹～X¹²At least two of which are the CR⁴And said R is⁴At least one is an electron-deficient group and at least one is an electron-donating group; preferably, the electron-deficient group is substituted or unsubstituted C₃～C₃₀Electron deficient heteroaryl, the electron donating group being selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₃～C₃₀One electron donating heteroaryl group.

7. A compound according to claim 1 or 6, wherein X is¹～X⁵Any one or more of (a) is CR⁴And the CR⁴In R⁴Is a group having an electron-deficiency as described above,

said X⁶～X¹²Any one or more of (a) is CR⁴And the CR⁴R in (1)⁴Is the electron donating group; or said X¹～X⁵Any one or more of (a) is CR⁴And the CR⁴R in (1)⁴Is the electron donating group, the X⁶～X¹²Any one or more of (a) is CR⁴And the CR⁴R in (1)⁴Is the electron deficient group.

8. A compound according to claim 6 or 7, wherein R is⁴The CR being the electron-deficient group⁴And said R⁴The CR being the electron-donating group⁴The absolute value of the number difference of (2) is less than or equal to 3;

preferably said R⁴Is the electron-deficient groupThe CR of the clique⁴And said R⁴The CR being the electron-donating group⁴The absolute value of the number difference of (a) is less than or equal to 1;

more preferably, said R⁴The CR being the electron-deficient group⁴And said R⁴The CR being the electron-donating group⁴The number difference of (2) is 0.

9. A compound according to any one of claims 6 to 8, wherein R is⁴The CR being the electron-deficient group⁴And said R⁴The CR being the electron-donating group⁴The number of the pairs is 1-2, preferably 1.

10. The compound of any one of claims 1 to 3 and 5 to 9, wherein the electron-deficient group is selected from any one of the following structures (II-1) to (II-4):

in the structural formula (II-1), Z¹、Z²、Z³、Z⁴And Z⁵Each independently selected from CR⁵Or an N atom, and Z¹、Z²、Z³、Z⁴And Z⁵At least one of which is an N atom,

in the structural formula (II-2), Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³Each independently selected from CR⁵Or an N atom, and Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³At least one of which is an N atom,

in the structural formula (II-3), Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³Each independently selected from CR⁵Or an N atom, and Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³At least one of which is an N atom,

in the structural formula (II-4), Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³Each independently selected from CR⁵Or an N atom, and Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³At least one of which is an N atom,

wherein R is⁵Is hydrogen, C₁～C₁₂Chain alkyl, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₃～C₃₀Any one of heteroaryl groups.

11. The compound of claim 10,

in the structural formula (II-1), Z¹、Z²、Z³、Z⁴And Z⁵At least two are N atoms;

in the structural formula (II-2), Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³At least two of which are N atoms;

the structureIn the formula (II-3), Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³At least two of which are N atoms;

in the structural formula (II-4), Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³At least two of which are N atoms.

12. The compound of claim 10, wherein the electron deficient group is selected from the group consisting of substituted or unsubstituted: any one of pyridyl, pyrimidyl, triazinyl, quinolyl, quinazolinyl and quinoxalinyl.

13. The compound of claim 12, wherein the substituents of said substituted pyridyl, pyrimidinyl, triazinyl, quinolinyl, quinazolinyl, quinoxalinyl groups are selected from the group consisting of: any one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl, phenanthryl and terphenyl.

14. The compound of claim 12, wherein the electron deficient group is selected from any one of the substituted or unsubstituted a 1-a 14 groups:

when the above groups have substituents, the substituents are selected from halogen and C₁～C₁₂Chain alkyl group of (1), C₃～C₁₂Cycloalkyl of, C₂～C₁₀Alkenyl radical, C₁～C₆Alkoxy or thioalkoxy of C₆～C₃₀Monocyclic aromatic hydrocarbon or condensed-ring aromatic hydrocarbon group of C₃～C₃₀Monocyclic or fused-ring heteroarenes ofOne or a combination of at least two of the above.

15. The compound of any one of claims 12 to 14, wherein the electron deficient group is selected from any one of the following groups B1 to B19:

16. a compound according to any one of claims 1, 6 to 9, wherein C, substituted or unsubstituted, in the electron donating group₃～C₃₀The electron-donating heteroaryl group is selected from the following substituted or unsubstituted groups: any one of dibenzofuran, dibenzothiophene and carbazole;

preferably any one of the following C1-C9 groups:

17. the compound of any one of claims 1 to 4,6 to 9, wherein said substituted or unsubstituted C₆～C₃₀Arylamino or said substituted or unsubstituted C₃～C₃₀The heteroaryl amino is selected from any one of the following D1-D15 groups:

18. according to claims 1 to 17The compound of any one of (1), wherein R is¹And R²Each independently selected from C₁～C₁₂Alkyl radical, C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₃₀An aryl group;

preferably methyl or substituted or unsubstituted phenyl.

19. A compound according to any one of claims 1 to 17, wherein R is³Is hydrogen.

20. The compound of claim 1, wherein the compound is selected from any one of the following structures:

21. use of a compound according to any one of claims 1, 2, 3,4, 17 to 20 as a hole transport material in an organic electroluminescent device.

22. Use of a compound according to any one of claims 1, 2, 3,5, 10 to 15, 18, 19, 20 as an electron transport material in an organic electroluminescent device.

23. Use of a compound according to any of claims 1, 6 to 20 as a material for a light-emitting layer in an organic electroluminescent device.

24. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, wherein the compound according to any one of claims 1 to 20 is contained in the organic layer.

Technical Field

The invention relates to the field of materials, in particular to a compound, application thereof and an organic electroluminescent device comprising the compound.

Background

In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them well suited for use in the manufacture of flexible substrates, allowing for the design and production of aesthetically pleasing and crunchy optoelectronic products on demand, with unparalleled advantages over inorganic materials. Examples of such sub-devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have been developed particularly rapidly, and have been commercially successful in the field of information display. The OLED can provide three colors of red, green and blue with high saturation, and a full-color display device manufactured by using the OLED does not need an additional backlight source and has the advantages of colorful, light, thin and soft color and the like.

The core of the OLED device is a thin film structure containing various organic functional materials. Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light.

People have developed various organic materials, and the organic materials are combined with various specific device structures, so that the carrier mobility can be improved, the carrier balance can be regulated and controlled, the electroluminescent efficiency can be broken through, and the attenuation of the device can be delayed. For quantum mechanical reasons, common fluorescent emitters mainly utilize singlet excitons generated when electrons and holes are combined to emit light, and are still widely applied to various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet excitons and singlet excitons, which are called phosphorescent emitters, and the energy conversion efficiency can be increased by up to four times as compared with conventional fluorescent emitters. The thermal excitation delayed fluorescence (TADF) technology can still effectively utilize triplet excitons to achieve higher luminous efficiency without using a metal complex by promoting the conversion of triplet excitons to singlet excitons. Thermal excitation sensitized fluorescence (TASF) technology also achieves higher luminous efficiency by sensitizing the emitter by means of energy transfer using a material with TADF properties.

As OLED products gradually enter the market, there are increasingly higher requirements on the performance of such products. The currently used OLED materials and device structures cannot meet the higher requirements of OLED products with respect to efficiency, lifetime, cost, etc.

Disclosure of Invention

The invention mainly aims to provide a compound, application thereof and an organic electroluminescent device comprising the compound, so as to solve the problem of low current efficiency of the compound in the prior art.

In the present specification, the expression of Ca to Cb represents that the group has carbon atoms a to b, and in general, the carbon atoms do not include the carbon atoms of the substituent in the expression "a group of substituted or unsubstituted Ca to Cb". If "substituted or unsubstituted" is not indicated, the number of carbon atoms is the number of carbon atoms of the whole group. In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of "deuterium" and "tritium" which are substantially chemically identical.

In the present specification, R in the similar structural formula¹The expression that the substituted bond(s) in (b) is directed to the center of the ring indicates that the substitution position may be at any possible position on the ring.

In the present specification, the alkyl group may be linear or branched, and is preferably 1 to 10 if the number of carbon atoms is not particularly specified. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and the like.

For example, in the present specification, examples of the aryl group having C6 to C30 include: phenyl, biphenyl, naphthyl, anthryl, phenanthryl, fluorenyl and the like, with phenyl, naphthyl and more preferably phenyl being preferred;

in this specification, a heteroaryl is an aryl group that contains more than one heteroatom from O, N, S, Si. Specific examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, and the like. Examples of the heteroaryl group having C3 to C30 include: nitrogen-containing heteroaryl, oxygen-containing heteroaryl, sulfur-containing heteroaryl, and the like, and specific examples thereof include: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, naphthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, indolyl, benzimidazolyl, indazolyl, imidazopyridinyl, benzotriazolyl, carbazolyl, furyl, thienyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, benzofuranyl, benzothienyl, benzoxazolyl, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzoxadiazolyl, benzothiadiazolyl, dibenzofuranyl, dibenzothienyl, piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like are preferred among them, pyridyl, dibenzofuranyl, piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like, Dibenzothienyl radical.

In order to achieve the above object, according to one aspect of the present invention, there is provided a compound having a structure represented by the following general formula (I):

wherein, X¹～X¹²Each independently is CR³Or CR⁴And at least one is CR⁴；R³Selected from hydrogen, C₁～C₁₂Chain alkyl, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino and substituted or unsubstituted C₆～C₃₀Any one of aryl groups; r⁴Selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₃～C₃₀Any one of heteroaryl; r¹And R²Each independently selected from C₁～C₁₂Chain alkyl, C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₃～C₃₀One of the heteroaryl groups, R¹R²Can form a ring; when the above groups have substituents, the substituents are selected from halogen and C₁～C₁₂Alkyl of (C)₃～C₁₂Cycloalkyl of, C₂～C₁₀Alkenyl radical, C₁～C₆Alkoxy or thioalkoxy of C₆～C₃₀Monocyclic aromatic hydrocarbon or condensed-ring aromatic hydrocarbon group of C₃～C₃₀Or a combination of at least two of the monocyclic or fused ring heteroaromatic hydrocarbon groups of (a).

Among the above compounds, compounds P1-P80 and P151-P156 are used as electron transport materials in organic electroluminescent devices.

Among the above compounds, compounds P81-P104, P139-P150, P157-P172 and P181-P183 are used as hole transport materials in organic electroluminescent devices.

Among the above compounds, compounds P105-P138 and P173-P180 are used as materials for light emitting layers in organic electroluminescent devices.

According to another aspect of the present invention there is provided a use of a compound as described above as a hole transport material in an organic electroluminescent device.

According to another aspect of the present invention, there is provided a use of the above compound as an electron transport material in an organic electroluminescent device.

According to another aspect of the present invention, there is provided a use of the above compound as a material for a light emitting layer in an organic electroluminescent device.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer containing a compound of any one of the above.

By applying the technical scheme of the invention, the fluorene compound with the 7-membered conjugated ring is introduced, so that the fluorene compound has a larger plane, the transmission barrier of a current carrier is reduced, the Tg (glass transition temperature) of a molecule is increased, the molecule has better thermodynamic stability, the rigidity of the molecule is enhanced by the design of a large conjugated structure, the chemical stability is enhanced, and even the device has better service life. Materials meeting various functional layers can be obtained by adjusting the electricity absorbing and supplying groups of the parent nucleus, and if the materials are substituted by the electricity absorbing groups, the materials can be used as electron transport layer materials; substituted with electron donating groups such as arylamine groups can be used as a hole transporting material; when the electroabsorption and power supply groups exist simultaneously, the transport of carriers is balanced, and the red phosphorescent material can be used as a luminescent layer material on a red phosphorescent host. Experiments prove that the compound is used in an organic electroluminescent device to enable the organic electroluminescent device to have the effects of low starting voltage and high luminous efficiency.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As analyzed in the background of the present application, the current efficiency of the compounds of the prior art has not yet reached the higher requirements of commercial OLEDs, and in order to solve this problem, the present application provides a compound, use and organic electroluminescent devices comprising the same.

In one exemplary embodiment of the present application, there is provided a compound having a structure represented by the following general formula (I):

wherein, X¹～X¹²Each independently is CR³Or CR⁴And at least one is CR⁴；R³Selected from hydrogen, C₁～C₁₂Chain alkyl, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino and substituted or unsubstituted C₆～C₃₀Any one of aryl groups; r⁴Selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₃～C₃₀Any one of heteroaryl; r¹And R²Each independently selected from C₁～C₁₂Alkyl radical, C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₃～C₃₀One of the heteroaryl groups, R¹And R²Can form a ring; when the above groups have substituents, the substituents are selected from halogen and C₁～C₁₂Alkyl of (C)₃～C₁₂Cycloalkyl of, C₂～C₁₀An alkenyl group,C₁～C₆Alkoxy or thioalkoxy of C₆～C₃₀Monocyclic aromatic hydrocarbon or condensed-ring aromatic hydrocarbon group of C₃～C₃₀Or a combination of at least two of the monocyclic or fused ring heteroaromatic hydrocarbon groups of (a).

The compound has strong structural stability, and can obtain a material meeting various functional layers by adjusting the electricity-absorbing and power-supplying groups of the parent nucleus, and the material can be used as an electron transport layer material if being substituted by the electricity-absorbing groups; substituted with electron donating groups such as arylamine groups can be used as a hole transporting material; when the electroabsorption and power supply groups exist simultaneously, the transport of carriers is balanced, and the red phosphorescent material can be used as a luminescent layer material on a red phosphorescent host. Experiments prove that the compound disclosed by the application is used in an organic electroluminescent device to enable the organic electroluminescent device to have the effects of low starting voltage and high luminous efficiency, and particularly when the compound is used as an electron transport layer material or a hole transport material in the organic electroluminescent device, the compound enables the organic electroluminescent device to have the effects of low starting voltage, high luminous efficiency and long service life.

In one embodiment of the present application, X is selected¹～X¹²At least one of which is CR⁴And wherein R is⁴Selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀A heteroarylamino group. The compound with the structure has strong hole transport capability, so that the compound can be used in a hole transport layer or an electron blocking layer of an organic electroluminescent device.

In order to further improve the hole transport ability of the compound, X is preferable¹～X¹²Middle CR⁴The number of (A) is 1 or 2, preferably X¹～X¹²Middle CR⁴The number of (2) is 1. In another embodiment, the CR is⁴At X⁴、X⁶～X⁸At any one or more of the sites, preferably CR⁴At X⁴、X⁶～X⁸Either or both of the sites, more preferably CR⁴At X⁴、X⁶～X⁸At the site ofAny one of them.

In another embodiment of the present application, X is¹～X¹²At least one of which is CR⁴And wherein R is⁴Selected from substituted or unsubstituted C₃～C₃₀Electron deficient heteroaryl. The compound with the structure has stronger electron transport capability, so that the compound can be used in an electron transport layer or a hole blocking layer of an organic electroluminescent device. In order to further improve electron transport ability, X is preferable¹～X¹²Middle CR⁴The number of (A) is 1 or 2, preferably X¹～X¹²Middle CR⁴The number of (2) is 1. In another embodiment, CR⁴At X⁴、X⁶～X⁸At any one or more of the sites, preferably CR⁴At X⁴、X⁶～X⁸Either or both of the sites, more preferably CR⁴At X⁴、X⁶～X⁸Any one of the loci.

In another embodiment of the present application, X is¹～X¹²At least two of which are CR⁴And R is⁴At least one is an electron-deficient group and at least one is an electron-donating group, preferably the electron-deficient group is a substituted or unsubstituted C₃～C₃₀Electron deficient heteroaryl, electron donating group selected from substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₃～C₃₀One of the electron-donating heteroaryl groups, the compound having the above structure has a strong ability to combine electrons and holes, and thus can be used in a light-emitting layer of an organic electroluminescent device.

In one embodiment, X is¹～X⁵Any one or more of (a) is CR having an electron-deficient group⁴And CR⁴R in (1)⁴Is an electron-deficient group, X⁶～X¹²Any one or more of (a) is CR having an electron-donating group⁴And CR⁴R in (1)⁴Is an electron donating group; or X¹～X⁵Any one or more of (a) is CR having an electron-donating group⁴And CR⁴R in (1)⁴For electron-donating groups, X⁶～X¹²Any one or more of (a) is CR having an electron-deficient group⁴And CR⁴R in (1)⁴Are electron deficient groups.

Furthermore, R is preferred⁴CR being electron-deficient groups⁴And R⁴CR being electron-donating groups⁴The absolute value of the number difference of (2) is not more than 3, more preferably not more than 1, i.e., R⁴CR being electron-deficient groups⁴And R⁴CR being electron-donating groups⁴On the basis of paired occurrence, controlling redundant R as much as possible⁴CR being electron-deficient groups⁴Or R⁴CR being electron-donating groups⁴Thereby making its electron and hole combining ability further controllable.

In one embodiment, R is preferably as defined above⁴CR being electron-deficient groups⁴And R⁴CR being electron-donating groups⁴The number of the pairs is 1 to 2, and 1 pair is more preferable. Thereby enabling more efficient electron and hole combination when the compound is applied to a light emitting layer.

In order to further improve the electron transport ability and maintain a low starting voltage and a high luminous efficiency, the electron-deficient group is selected from any one of the following structures (II-1) to (II-4):

in the structural formula (II-1), Z¹、Z²、Z³、Z⁴And Z⁵Each independently selected from CR⁵Or an N atom, and Z¹、Z²、Z³、Z⁴And Z⁵At least one of which is an N atom; in the structural formula (II-2), Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³Each independently selected from CR⁵Or an N atom, and Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³At least one of which is an N atom; in the structural formula (II-3), Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³Each independently selected from CR⁵Or an N atom, and Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³At least one of which is an N atom; in the structural formula (II-4), Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³Each independently selected from CR⁵Or an N atom, and Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³At least one of them being a N atom, wherein R is⁵Is hydrogen, C₁～C₁₂Alkyl radical, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substituted or unsubstituted C₆～C₃₀Arylamino, substituted or unsubstituted C₃～C₃₀Heteroarylamino, substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₃～C₃₀Any one of heteroaryl groups.

In order to improve the hole transport ability of the above electron-deficient group, it is preferable that, in the structural formula (II-1), Z¹、Z²、Z³、Z⁴And Z⁵At least two are N atoms; preferably, in the formula (II-2), Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²And Z¹³At least two of which are N atoms; preferably, in the formula (II-3), Z¹⁴、Z¹⁵、Z¹⁶、Z¹⁷、Z¹⁸、Z¹⁹、Z²⁰、Z²¹、Z²²And Z²³At least two of which are N atoms; preferably, in the formula (II-4), Z²⁴、Z²⁵、Z²⁶、Z²⁷、Z²⁸、Z²⁹、Z³⁰、Z³¹、Z³²And Z³³At least two of which are N atoms.

In one embodiment, at R⁴The electron-deficient group is selected from any one of substituted or unsubstituted pyridyl, pyrimidyl, triazinyl, quinolyl, quinazolinyl and quinoxalinyl, and more preferably triazinyl, quinazolinyl or quinoxalinyl, on the basis of the structures represented by the structural formulae (II-1) to (II-4).

The substituent of the substituted pyridyl, pyrimidyl, triazinyl, quinolyl, quinazolinyl and quinoxalinyl group is preferably any one selected from the group consisting of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, pyridyl, phenanthryl and terphenyl.

Or preferably the electron-deficient group is selected from any one of substituted or unsubstituted A1-A14 groups:

when the above groups have substituents, the substituents are selected from halogen and C₁～C₁₂Alkyl of (C)₃～C₁₂Cycloalkyl of, C₂～C₁₀Alkenyl radical, C₁～C₆Alkoxy or thioalkoxy of C₆～C₃₀Monocyclic aromatic hydrocarbon or condensed-ring aromatic hydrocarbon group of C₃～C₃₀Or a combination of at least two of the monocyclic or fused ring heteroaromatic hydrocarbon groups of (a).

More specifically, the electron-deficient group is any one selected from the group consisting of groups B1 to B19:

in one embodiment, C in the above electron donating group is substituted or unsubstituted₃～C₃₀The electron-donating heteroaryl group is selected from the following substituted or unsubstituted groups: any one of dibenzofuran, dibenzothiophene and carbazole; more preferably any one of the following C1-C9 groups:

further, the above-mentioned substituted or unsubstituted C₆～C₃₀Arylamino or substituted or unsubstituted C₃～C₃₀The heteroaryl amino is selected from any one of the following D1-D15 groups:

preferably, regardless of the CR described above⁴Selected from any of the above groups, R above¹And R²Is independently selected from C₁～C₁₂Alkyl radical, C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₃₀The aryl group is more preferably a methyl group or a substituted or unsubstituted phenyl group, or a phenyl group and the phenyl groups are connected to form a five-membered ring.

In one embodiment, R is preferably as defined above³Is hydrogen.

In specific embodiments, the compound is selected from any one of the following:

in another exemplary embodiment of the present application, there is provided a use of the compound of any one of the above as a material of a light emitting layer or as a hole transporting material or as an electron transporting material in an organic electroluminescent device. Wherein the compound with hole transport capability is selected to be applied to a hole transport material in an organic electroluminescent device, the compound with electron transport capability is selected to be applied to an electron transport material in the organic electroluminescent device, or the compound with hole and electron combination capability is selected to be applied to a material of a light emitting layer in the organic electroluminescent device.

Such as: among the above compounds, compounds P1-P80 and P151-P156 are used as electron transport materials in organic electroluminescent devices; among the above compounds, compounds P81-P104, P139-P150, P157-P172 and P181-P183 are used as hole transport materials in organic electroluminescent devices; among the above compounds, compounds P105-P138 and P173-P180 are used as materials for light emitting layers in organic electroluminescent devices.

In still another exemplary embodiment of the present application, there is provided an organic electroluminescent device including a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer containing a compound of any one of the above.

Due to the strong structural stability of the compound, materials meeting various functional layers can be obtained by adjusting the electricity-absorbing and power-supplying groups of the parent nucleus, and the compound can be used as an electron transport layer material if being substituted by the electricity-absorbing groups; substituted with electron donating groups such as arylamine groups can be used as a hole transporting material; when the electroabsorption and power supply groups exist simultaneously, the transport of carriers is balanced, and the red phosphorescent material can be used as a luminescent layer material on a red phosphorescent host.

Preferably, an electron blocking layer is provided between the hole transporting layer and the light emitting layer of the organic electroluminescent device, and the electron blocking layer contains a compound which is the above-mentioned compound having hole transporting ability. Preferably, a hole-blocking layer is provided between the light-emitting layer and the electron-transporting layer, and the hole-blocking layer contains another compound having an electron-transporting ability.

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The invention relates to a mother nucleus synthesis route of a compound shown in a structural general formula (I):

different target compounds can be obtained by substituting different substituents. Wherein X1 to X12 represent halogen, trifluoromethanesulfonate or hydrogen, and R is¹、R²R in the general structural formula (I)¹、R²By definition, the two may be bonded to each other. In the above synthesis method, substituent R is coupled by Buchwald-Hartwig coupling⁴The linker may be attached to the parent nucleus by any method known to those skilled in the art, including, but not limited to, Ullmann's coupling, Grignard reagent, and SUZUKI, and any equivalent synthetic method may be used as necessary to attach the substituent to the parent nucleus.

More specifically, the combination of several intermediate parent nucleus is as follows:

1) synthesis of M1

Step 1), adding 1-bromo-2-methyl naphthoate (100mmol), o-bromobenzoic acid (100mmol), tetrakis (triphenylphosphine) palladium (1 mmol), potassium carbonate (120mmol), water (50 ml) and dioxane (300ml) into a reaction bottle, reacting for 4h at 80 ℃ under the protection of nitrogen, completely extracting with dichloromethane, and concentrating to obtain an intermediate M1-1.

Step 2), adding M1-1(50mmol), 2-aminophenylboronic acid pinacol ester (50mmol), tetrakis (triphenylphosphine) palladium (1 mmol), potassium carbonate (60mmol), water (30 ml) and dioxane (200ml) into a reaction bottle, reacting for 5 hours at 120 ℃ under the protection of nitrogen, extracting by dichloromethane after the reaction is completed, and concentrating and purifying by column chromatography to obtain an intermediate M1-2.

And 3) adding M1-2(40mmol), acetic acid 100ml and sulfuric acid 15ml into a reaction bottle, cooling to 0 ℃, slowly adding an aqueous solution of sodium nitrite (50mmol) dropwise, after complete reaction, slowly pouring the reaction solution into water, filtering, and purifying a filter cake column chromatography to obtain an intermediate M1-3.

And 4), adding M1-3(30mmol) into THF (200ml), dropwise adding 1mol/L methyl magnesium bromide (90ml) at 0 ℃, reacting at room temperature for 3h after dropwise adding, monitoring by TLC to complete the reaction, adding diluted hydrochloric acid to quench, extracting an organic phase by using dichloromethane, and concentrating to obtain an intermediate M1-4.

And step 5), adding M1-4(25mmol) and 100ml of dichloromethane into a reaction bottle, cooling to 0 ℃, dropwise adding methanesulfonic acid (30mmol), reacting at room temperature for 2 hours after dropwise adding, completely reacting, adding water, and extracting and concentrating with dichloromethane to obtain M1-5.

And 6), adding M1-5(20mmol) into DMF, cooling to 0 ℃, dropwise adding a DMF solution of NBS (24mmol), carrying out heat preservation reaction for 2 hours after dropwise adding, monitoring the reaction completion by GC-MS, slowly pouring the final reaction liquid into water, filtering, washing a filter cake by ethanol, and drying to obtain an intermediate M1.

Validation of intermediate M1:¹H NMR(500MHz,Chloroform)δ8.53(dd,J＝7.5,1.4Hz,1H),8.46–8.34(m,2H),8.16–8.05(m,3H),7.92(s,1H),7.82(t,J＝7.5Hz,1H),7.38–7.27(m,2H),7.27–7.18(m,1H),1.75(s,6H).

2) synthesis of M2:

the synthesis of M2 was the same as that of M1 except that methyl magnesium bromide in step 4) was replaced with an equivalent amount of phenyl magnesium bromide. Intermediate M2 was obtained.

Validation of intermediate M2:¹H NMR(500MHz,Chloroform)δ8.56(dd,J＝7.4,1.5Hz,1H),8.47–8.35(m,2H),8.18–8.06(m,4H),7.86(t,J＝7.4Hz,1H),7.36–7.21(m,7H),7.22–7.14(m,2H),7.10(dd,J＝7.5,1.5Hz,4H).

3) synthesis of M3:

step 1), M3-1 was synthesized as M1-1 except that methyl 1-bromo-2-naphthoate was replaced with an equivalent amount of 1-bromo-2-naphthoic acid.

Step 2), adding M3-1(50mmol), 2-aminophenylboronic acid pinacol ester (50mmol), tetrakis (triphenylphosphine) palladium (1 mmol), potassium carbonate (60mmol), water (30 ml) and dioxane (200ml) into a reaction bottle, reacting for 5 hours at 120 ℃ under the protection of nitrogen, extracting by using dichloromethane after complete reaction, and concentrating and purifying by column chromatography to obtain an intermediate M3-2.

And 3) adding M3-2(40mmol), acetic acid 100ml and sulfuric acid 15ml into a reaction bottle, cooling to 0 ℃, slowly adding an aqueous solution of sodium nitrite (50mmol) dropwise, after complete reaction, slowly pouring the reaction solution into water, filtering, and purifying a filter cake column chromatography to obtain an intermediate M3-3.

And 4) adding M3-3(30mmol) and 100ml of polyphosphoric acid to 100 ℃, reacting for 2 hours, monitoring the reaction by TLC, slowly pouring the reaction liquid into water, extracting and concentrating by dichloromethane, and purifying by column chromatography to obtain an intermediate M3-4.

And step 5), adding M3-4(20mmol) into DMF, cooling to 0 ℃, then dropwise adding a DMF solution of NBS (24mmol), carrying out heat preservation reaction for 2 hours after dropwise adding, monitoring the reaction completion by adopting GC-MS, slowly pouring the reaction liquid into water, filtering, washing a filter cake by using ethanol, and drying to obtain an intermediate M3-5.

And step 6), adding 2-bromobiphenyl (20mmol) into THF, cooling to-78 ℃, dropwise adding n-butyllithium (24mmol), after dropwise adding, carrying out heat preservation reaction for 0.5h, quickly dropwise adding a THF solution of M3-5 into the reaction solution, carrying out heat preservation reaction for 1h, recovering to react at room temperature for 3h, adding water for quenching, extracting with ethyl acetate, and concentrating to obtain an intermediate M3-6.

And step 7), adding M3-6(25mmol) and 100ml of dichloromethane into a reaction bottle, cooling to 0 ℃, dropwise adding methanesulfonic acid (30mmol), reacting at room temperature for 2 hours after dropwise adding, completely reacting, adding water, and extracting and concentrating with dichloromethane to obtain M3.

Validation of intermediate M3:¹H NMR(500MHz,Chloroform)δ8.56(dd,J＝7.4,1.5Hz,1H),8.46–8.38(m,2H),8.11(qd,J＝7.5,2.8Hz,3H),7.89(ddd,J＝23.1,11.7,7.3Hz,4H),7.57(dd,J＝7.5,1.4Hz,2H),7.41–7.28(m,4H),7.24(ddd,J＝7.5,4.7,1.6Hz,3H).

4) synthesis of M4:

synthesis of M4 was the same as that of intermediate M1 except that M1-1 was replaced with equivalent M3-1.

Validation of intermediate M4:¹H NMR(500MHz,Chloroform)δ8.53(dd,J＝14.9,3.0Hz,1H),8.47–8.36(m,2H),8.16–8.04(m,3H),7.92(s,1H),7.82(t,J＝15.0Hz,1H),7.53(d,J＝3.1Hz,1H),7.36(d,J＝2.9Hz,1H),1.75(s,6H).

5) synthesis of M5

M5 was synthesized in the same manner as M2 except that o-chlorobenzeneboronic acid was replaced with 2-bromo-4-chlorobenzeneboronic acid in equivalent amount.

Validation of intermediate M5:¹H NMR(500MHz,Chloroform)δ8.56(dd,J＝14.9,3.0Hz,1H),8.48–8.33(m,2H),8.11(ddd,J＝17.1,12.0,4.6Hz,4H),7.86(t,J＝15.0Hz,1H),7.53(d,J＝3.1Hz,1H),7.36(d,J＝2.9Hz,1H),7.32–7.13(m,6H),7.13–7.02(m,4H).

6) synthesis of M6

M6 was synthesized as M3 except that o-chlorobenzeneboronic acid was replaced with an equivalent of 2-bromo-4-chlorobenzeneboronic acid.

Validation of intermediate M6:¹H NMR(500MHz,Chloroform)δ8.56(s,1H),8.42(s,2H),8.11(d,J＝10.0Hz,3H),7.96–7.80(m,4H),7.54(d,J＝14.5Hz,3H),7.35(d,J＝8.6Hz,3H),7.24(s,2H).

the following are specific compoundsSynthetic examples

Synthesis example 1:

synthesis of Compound P35

M1(100mmol), pinacol diboron (120mmol), potassium acetate (150mmol), dioxane (300ml), Pd (dppf) Cl₂0.4g of the reaction solution is added into a reaction bottle and heated until reflux reaction is carried out for 5 hours, TLC monitors the reaction completion, and the reaction solution is poured into water and extracted and concentrated by dichloromethane to obtain P35-A.

Mixing P35-A (80mmol) and 2- ([1,1' -biphenyl)]-4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (100mmol), potassium carbonate (50mmol), Pd (PPh)₃)₄0.5g, 50ml of water and 300ml of dioxane are added into a reaction bottle, the mixture is heated until reflux reaction is carried out for 5 hours, TLC monitors the completion of the reaction, a large amount of solid is separated out after the temperature is reduced, the mixture is directly filtered, and a filter cake is dried by ethanol and then recrystallized by toluene to obtain a compound P35.

Validation of compound P35:¹H NMR(500MHz,Chloroform)δ8.85(dd,J＝14.9,3.0Hz,1H),8.54–8.29(m,5H),8.17(s,1H),8.15–8.04(m,2H),8.01–7.90(m,2H),7.81–7.63(m,3H),7.57–7.35(m,6H),7.33(dd,J＝13.5,7.4Hz,2H),7.29–7.19(m,3H),1.75(s,6H).

synthesis example 2:

synthesis of Compound P48

The procedure is as in synthesis example 1, except that 2- ([1,1' -biphenyl ] -4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine is replaced with an equivalent amount of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and M1 is replaced with an equivalent amount of M2 to give compound P48.

Validation of compound P48:¹H NMR(500MHz,Chloroform)δ8.84(dd,J＝15.0,2.9Hz,1H),8.47–8.28(m,9H),8.16–8.03(m,2H),7.78–7.56(m,4H),7.54–7.43(m,6H),7.37–7.03(m,13H).

synthetic example 3:

synthesis of Compound P61

The procedure is as in synthesis example 1, except that 2- ([1,1' -biphenyl ] -4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine is replaced with an equivalent amount of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and M1 is replaced with an equivalent amount of M3 to give compound P61.

Validation of compound P61:¹H NMR(500MHz,Chloroform)δ8.84(dd,J＝15.0,2.9Hz,1H),8.50–8.27(m,7H),8.18–8.03(m,2H),8.01–7.84(m,4H),7.76–7.62(m,4H),7.57–7.44(m,6H),7.40–7.16(m,9H).

synthetic example 4:

synthesis of Compound P83

Mixing M1(50mmol), N-phenyl- [1,1' -biphenyl ] group]-4-amine (50mmol), sodium tert-butoxide (60mmol), toluene (200ml), Pd₂(dba)₃0.4g of S-Phos0.4g are added into a reaction flask, the mixture is heated to reflux reaction for 5 hours, TLC monitors the completion of the reaction, and after the reaction solution is poured into water, dichloromethane is adopted for extraction and concentration to obtain the compound P83.

Validation of compound P83:¹H NMR(500MHz,Chloroform)δ8.52–8.36(m,3H),8.16–8.03(m,3H),7.80–7.65(m,3H),7.61(s,1H),7.59–7.29(m,9H),7.28–7.18(m,3H),7.13–6.88(m,3H),1.75(s,6H).

synthesis example 5:

synthesis of Compound P89

The procedure of Synthesis example 1 was followed except that 2-phenyl-4- [1,1' -biphenyl ] -1,3, 5-triazine was replaced with an equivalent amount of 4-bromotriphenylamine, and M1 was replaced with an equivalent amount of M2 to give compound P89.

Validation of compound P89:¹H NMR(500MHz,Chloroform)δ8.84(dd,J＝15.0,2.9Hz,1H),8.49–8.33(m,3H),8.18–8.03(m,2H),7.69(dd,J＝25.1,10.1Hz,2H),7.60–7.51(m,2H),7.42–7.13(m,15H),7.13–6.94(m,10H).

synthetic example 6:

synthesis of Compound P92

The procedure of Synthesis example 1 was followed except that 2-phenyl-4- [1,1' -biphenyl ] -1,3, 5-triazine was replaced with N- (4-bromophenyl-) -N ' -phenyl- [1,1' -biphenyl ] in an equivalent amount, and M1 was replaced with M3 in an equivalent amount, to obtain Compound P92.

Validation of compound P92:¹H NMR(500MHz,Chloroform)δ8.84(dd,J＝15.0,2.9Hz,1H),8.49–8.32(m,3H),8.17–8.02(m,2H),7.90(dd,J＝14.7,3.2Hz,2H),7.80–7.61(m,6H),7.60–7.29(m,15H),7.29–7.17(m,5H),7.14–6.93(m,3H).

synthesis example 7:

synthesis of Compound P107

Mixing M4(50mmol), N-phenyl- [1,1' -biphenyl ] group]-4-amine (50mmol), sodium tert-butoxide (60mmol), toluene (200ml), Pd₂(dba)₃0.4g of S-Phos and 0.4g of S-Phos are added into a reaction bottle, the mixture is heated to 80 ℃ to react for 5 hours, TLC monitors the reaction completion, and after the reaction liquid is poured into water, dichloromethane is adopted for extraction and concentration, so that an intermediate PH107-A is obtained.

Intermediate P107-A (30mmol), pinacol diboron (120mmol), potassium acetate (150mmol), dioxane (300ml), Pd (dba)₃0.3g of S-Phos and 0.4g of S-Phos are added into a reaction bottle, the mixture is heated until reflux reaction is carried out for 5 hours, TLC monitors the reaction completion, and after the reaction liquid is poured into water, dichloromethane is adopted for extraction and concentration, so that an intermediate P107-B is obtained.

Intermediate P107-B (20mmol), 2-chloro-4-phenylquinazoline (20mmol), potassium carbonate (30mmol), Pd (PPh)₃)₄Adding 0.2g of the compound P107, 20ml of water and 150ml of dioxane into a reaction bottle, heating until reflux reaction is carried out for 5 hours, monitoring by TLC to finish the reaction, separating out a large amount of solid after cooling, directly filtering, drying a filter cake by ethanol, and recrystallizing by toluene to obtain the compound P107.

Validation of compound P107:¹H NMR(500MHz,Chloroform)δ9.33(d,J＝3.1Hz,1H),8.51–8.36(m,3H),8.20–8.03(m,4H),7.96(dd,J＝14.9,3.0Hz,1H),7.86–7.59(m,10H),7.59–7.32(m,9H),7.30–7.18(m,2H),7.14–6.92(m,3H),1.75(s,6H).

synthesis example 8:

synthesis of Compound P123

Mixing M4(50mmol), pinacol diborate (60mmol), potassium acetate (60mmol), dioxane (200ml), Pd (dppf) Cl₂Adding 0.3g of the mixture into a reaction bottle, heating the mixture until reflux reaction is carried out for 4 hours, monitoring the reaction completion by TLC, pouring the reaction liquid into water, and then extracting and concentrating the reaction liquid by using dichloromethane to obtain an intermediate P123-A.

Intermediate P123-A (30mmol), 2-chloro-4-phenylquinazoline (50mmol), potassium carbonate (30mmol), Pd (PPh)₃)₄Adding 0.3g, 20ml of water and dioxane (150ml) into a reaction bottle, heating until reflux reaction is carried out for 4 hours, monitoring by TLC to complete the reaction, cooling, extracting by ethyl acetate, and concentrating the obtained organic phase to obtain an intermediate P123-B.

Intermediate P123-B (20mmol), triphenylamine 4-boronic acid, potassium phosphate (30mmol), xylene (150ml), Pd₂(dba)₃0.3g of S-Phos0.3g are added into a reaction flask, heated to 150 ℃ for reaction for 10h, and the reaction is monitored by TLCAfter completion, the reaction solution was poured into water, extracted and concentrated with dichloromethane, and then recrystallized with toluene to obtain a purified compound P123.

Validation of compound P123:¹H NMR(500MHz,Chloroform)δ8.91–8.79(m,2H),8.54–8.34(m,3H),8.20–8.05(m,4H),8.01(dd,J＝14.8,3.1Hz,1H),7.86–7.59(m,7H),7.59–7.42(m,4H),7.41–7.32(m,2H),7.29–7.16(m,4H),7.14–6.90(m,6H),1.75(s,6H).

synthetic example 9:

synthesis of Compound P119

The procedure was as in Synthesis example 7, except that M4 was replaced with equivalent amount of M5, N-phenyl- [1,1' -biphenyl ] -4-amine was replaced with equivalent amount of diphenylamine, and 2-chloro-4-phenylquinazoline was replaced with equivalent amount of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, to give Compound P119.

Validation of compound P119:¹H NMR(500MHz,Chloroform)δ9.57(d,J＝2.9Hz,1H),8.57–8.28(m,7H),8.20–7.98(m,3H),7.86–7.66(m,2H),7.58–7.42(m,6H),7.32–7.13(m,10H),7.13–6.93(m,11H).

synthetic example 10:

synthesis of Compound P135

The procedure was as in synthesis example 8 except that triphenylamine-4-boronic acid was replaced with N-phenyl-carbazole-3-boronic acid in an equivalent amount to give compound P135.

Validation of compound P135:¹H NMR(500MHz,Chloroform)δ9.04(d,J＝2.9Hz,1H),8.85(dd,J＝14.9,3.0Hz,1H),8.62–8.34(m,4H),8.29(d,J＝2.9Hz,1H),8.20–8.05(m,4H),8.01(dd,J＝14.9,3.0Hz,1H),7.87–7.40(m,17H),7.13(pd,J＝15.0,3.6Hz,2H),1.75(s,6H).

device embodiments

Detailed description of the preferred embodiments

The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.

In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.

The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used₂) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.

The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.

The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).

In one aspect of the present invention, the hole transport region material may be selected from one or more compounds represented by the general structural formula (I) of the present invention, and may also be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenes, polyaniline/dodecylbenzene sulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds represented by HT-1 to HT-34 below; or any combination thereof.

The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI-1-HI-3 described below.

The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.

According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer can be selected from one or more compounds shown in the structural general formula (I) of the invention, and can also be selected from, but not limited to, one or more combinations of GPH-1 to GPH-80.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more of GPD-1 to GPD-47 listed below.

Wherein D is deuterium.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.

The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

In one aspect of the present invention, the electron transport layer material may be selected from one or more compounds represented by the general structural formula (I) of the present invention, and may also be selected from, but is not limited to, one or more combinations of ET-1 to ET-57 listed below.

An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li₂O、Cs₂CO₃、BaO、Na、Li、Ca。

In the above device embodiments, at least one of the organic material layers, whether it is a hole transport region, a light emitting layer, or an electron transport region, is provided with the compound of the present application.

The structures of some of the compounds used in the following comparative examples of devices according to the invention are as follows:

the organic electroluminescent device in this example was prepared as follows.

Device example 1

The glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams; placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10^-5Pa, performing vacuum thermal evaporation on the anode layer film in sequence to obtain a 10nm HT-4: HIL-3(97/3, w/w) mixture as a hole injection layer, a 60nm compound P83 as a hole transport layer, a 40nm compound GPH-62: RPD-8(100:3, w/w) binary mixture as a light emitting layer, a 25nm compound ET-46: ET-57(50/50, w/w) mixture as an electron transport layer, 1nm LiF as an electron injection layer, and 150nm metal aluminum as a cathode. The total evaporation rate of all the organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.

Device example 2

Device example 2 was fabricated in the same manner as device example 1 except that P83 in the hole transport layer was replaced with P89.

Device example 3

Device example 2 was fabricated in the same manner as device example 1 except that P83 in the hole transport layer was replaced with P92.

Comparative device example 1

Device comparative example 1 was fabricated in the same manner as in device example 1 except that P83 in the light-emitting layer was replaced with C1.

Method of testing the device (including equipment and test conditions):

the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:

using digital source meter and brightness under the same brightnessThe driving voltage and current efficiency of the organic electroluminescent devices prepared in device examples 1 to 3 and device comparative example 1 and the lifetime of the devices were measured by a meter, and the test results are shown in table 1. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 3000cd/m²The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 10000cd/m²The luminance drop of the organic electroluminescent device was measured to be 9500cd/m by maintaining a constant current at luminance²Time in hours.

TABLE 1

Device example 4

The difference from device example 1 is that 60nm of compound HT-4 served as the hole transport layer and 25nm of a mixture of compound P35: ET-57(50/50, w/w) served as the electron transport layer.

Device example 5

Device example 5 was fabricated in the same manner as device example 4 except that P35 in the electron transport layer was replaced with P48.

Device example 6

Device example 6 was fabricated in the same manner as device example 4 except that P35 in the electron transport layer was replaced with P61.

Comparative device example 2

Device comparative example 2 was fabricated in the same manner as device example 4 except that P35 in the electron transport layer was replaced with C2.

The driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in device examples 4 to 6 and device comparative example 2 were measured according to the device test method described above. Device organic electroluminescent device properties are given in table 2 below.

TABLE 2

Device example 7

The difference from device example 1 is that 60nm of compound HT-4 is used as a hole transport layer and 40nm of compound P107: RPD-8(100:3, w/w) binary mixture is used as a light emitting layer.

Device example 8

Device example 8 was fabricated in the same manner as device example 7 except that P107 in the light-emitting layer was replaced with P119.

Device example 9

Device example 8 was fabricated in the same manner as device example 7 except that P107 in the light-emitting layer was replaced with P123.

Device example 10

Device example 8 was fabricated in the same manner as device example 7 except that P107 in the light-emitting layer was replaced with P135.

Comparative device example 3

Device comparative example 3 was fabricated in the same manner as in device example 7 except that P107 in the light-emitting layer was replaced with C3.

The driving voltage and current efficiency of the organic electroluminescent devices prepared in device examples 7 to 10 and device comparative example 3 were measured according to the device test method described above. Device organic electroluminescent device properties are given in table 3 below.

TABLE 3

The results show that the compound provided by the invention is used for an organic electroluminescent device, can effectively reduce the take-off and landing voltage, and can improve the current efficiency.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.