阅读说明：本技术 一种化合物及其应用 (Compound and application thereof ) 是由 邢其锋 李之洋 黄鑫鑫 高月 于 2018-07-24 设计创作，主要内容包括：本发明保护一种新型化合物及其应用,所述化合物如下述式(1)所示：<Image he="360" wi="700" file="DDA0001740404470000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中：A代表与母核并环连接的基团,选自C<Sub>3</Sub>-C<Sub>30</Sub>的杂环芳基；Y<Sub>1</Sub>-Y<Sub>8</Sub>选自C或者N；X选自O、S、NR、或CR’R”中的一种；上述R、R’和R”分别独立选自C<Sub>1</Sub>-C<Sub>10</Sub>的烷基、取代或未取代的C<Sub>6</Sub>-C<Sub>30</Sub>的芳基、取代或未取代的C<Sub>3</Sub>-C<Sub>30</Sub>的杂环芳基中的一种；Ar选自取代或未取代的C<Sub>6</Sub>-C<Sub>30</Sub>的芳基、取代或未取代的C<Sub>3</Sub>-C<Sub>30</Sub>的杂环芳基中的一种；R<Sup>1</Sup>、R<Sup>2</Sup>和R<Sup>3</Sup>分别独立选自H、C<Sub>1</Sub>-C<Sub>10</Sub>的烷基、取代或未取代的C<Sub>6</Sub>-C<Sub>30</Sub>芳基、取代或未取代的C<Sub>3</Sub>-C<Sub>30</Sub>杂环芳基中的一种；m和n分别独立选自0-4整数,p选自0-2的整数。本发明的化合物作为OLED器件中的发光材料时,表现出优异的器件性能和稳定性。本发明同时保护采用上述通式化合物的有机电致发光器件。(The invention protects a novel compound, the use thereof, and the use thereofThe compound is represented by the following formula (1): wherein: a represents a group which is linked to the mother nucleus and is selected from C 3 ‑C 30 The heterocyclic aryl group of (a); y is 1 ‑Y 8 Selected from C or N; x is selected from O, S, NR or CR 'R'; r, R 'and R' are each independently selected from C 1 ‑C 10 Alkyl, substituted or unsubstituted C 6 ‑C 30 Aryl, substituted or unsubstituted C 3 ‑C 30 One of the heterocyclic aryl groups of (a); ar is selected from substituted or unsubstituted C 6 ‑C 30 Aryl, substituted or unsubstituted C 3 ‑C 30 One of the heterocyclic aryl groups of (a); r 1 、R 2 And R 3 Each independently selected from H, C 1 ‑C 10 Alkyl, substituted or unsubstituted C 6 ‑C 30 Aryl, substituted or unsubstituted C 3 ‑C 30 One of heterocyclic aryl; m and n are independently selected from integers of 0-4, and p is selected from integers of 0-2. The compound of the present invention shows excellent device performance and stability when used as a light emitting material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.)

1. A compound of the formula (1):

in formula (1):

a represents a group which is linked to the mother nucleus and is selected from C₃-C₃₀The heterocyclic aryl group of (a);

Y₁-Y₈selected from C or N; x is selected from O, S, NR or CR 'R'; r, R 'and R' are each independently selected from C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

ar is selected from substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

R¹、R²and R³Each independently selected from H, C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of heterocyclic aryl; r¹、R²And R³Each independently can be connected with the connected mother core structure to form a ring;

m and n are independently selected from integers of 0-4, and p is selected from integers of 0-2.

When the above groups have substituents, the substituents are respectively and independently selected from halogen and C₁-C₁₀Alkyl or cycloalkyl of, C₂-C₁₀Alkenyl radical, C₁-C₆Alkoxy or thioalkoxy group of (C)₆-C₃₀Monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon group of (A), C₃-C₃₀One of the monocyclic heteroaromatic group or the condensed ring heteroaromatic group of (a).

2. The compound of general formula (la) according to claim 1, wherein a in formula (1) is selected from one of the following formulae (2-1) to (2-5):

wherein, Y₉-Y₃₆Selected from CR 'or N, R' being as defined in formula (1);

indicates the position of the bond.

3. A compound of formula (la) according to claim 2, wherein:

in the formula (2-1), Y₉-Y₁₄At least one of which is N;

in the formula (2-2), Y₁₅-Y₂₀At least one of which is N;

in the formula (2-3), Y₂₁-Y₂₈At least one of which is N;

in the formula (2-4), Y₂₉-Y₃₆At least one of which is N;

in the formula (2-5), Y₂₉-Y₃₆At least one of which is N.

4. Compounds of general formula (la) according to claim 1, wherein formula (1) is selected from the following structural compounds of formulae (3-1) to (3-2):

in the formulae (3-1) and (3-2): y is₁-Y₈、X、Ar、R¹、R²、R³And m, n and p are each as defined in the general formula (1).

5. A compound of general formula (la) according to claim 1 or 4, wherein in formula (1), formula (3-1) to formula (3-2):

ar is selected from the following groups: phenyl, biphenyl, terphenyl, naphthyl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, carbazolyl, azacarbazolyl, anthracenyl, fluoranthenyl.

6. A compound of formula (la) according to claim 1, selected from the compounds of the following specific structures:

7. use of a compound of formula (la) according to claim 1 or 4 as a light-emitting host material in an organic electroluminescent device.

8. Use of the structural compound according to claim 6 as a light-emitting host material in an organic electroluminescent device.

9. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound of formula (la) according to any one of claims 1 or 4.

10. The organic electroluminescent device according to claim 9, wherein the compound of the formula included in the organic layer is selected from compounds of the following specific structures:

Technical Field

The present invention relates to a novel compound of the general formula which can be used as a host material of a light emitting layer of an organic electroluminescent device or an electron transport material, and an organic electroluminescent device using the same.

Background

Since the chinese scientist professor dunqing cloud reported the electroluminescence phenomenon of organic compounds for the first time, organic electroluminescent diodes (OLEDs) have attracted much attention due to their advantages of self-luminescence, high contrast, low power consumption, etc.

At present, blue fluorescence is generally adopted in combination with red and green phosphorescent materials in the organic electroluminescent device structure in the display and illumination field. The light emitting layer of a common electroluminescent device mainly adopts a host-guest doping mode to adjust the light color, the brightness and the efficiency, thereby improving the performance of the device.

The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage direct current drive, full curing, wide viewing angle, light weight, simple composition and process and the like, and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle, low power, 1000 times of response speed of the liquid crystal display, and lower manufacturing cost than the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.

With the continuous advance of the OLED technology in the two fields of illumination and display, people pay more attention to the research of efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of the device structure and various organic materials. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. The phosphorescent host materials used at present have single carrier transport capability, such as hole-based transport hosts and electron-based transport hosts. The single carrier transport ability causes mismatching of electrons and holes in the light emitting layer, resulting in severe roll-off of efficiency and shortened lifetime. At present, in the use process of a phosphorescent host, a bipolar material or a double-host material matching mode is adopted to solve the problem of unbalanced carriers of a single-host material. The bipolar material realizes the common transmission of electrons and holes in one compound, and the molecular structure is more complex; the double-main-body material is used for realizing the transmission and combination of electrons and holes in the luminous layer by matching two materials, wherein one material is used as an electron type material, the other material is used as a hole type material, the electrons and the holes are combined at an interface after being conducted by the two materials, the two materials have wider sources, and the better device performance can be realized by adopting a combination mode of different materials. The existing organic electroluminescent materials still have room for improvement in light-emitting properties, and development of new organic electroluminescent materials is urgently needed in the industry.

Disclosure of Invention

The invention aims to solve the problems of weak electron transport capability and unbalanced carrier transport in the prior art, provides a novel general formula compound with good electron transport capability, and simultaneously provides an organic electroluminescent device adopting the novel compound.

The compound of the present invention is represented by the following general formula (1):

in formula (1):

a represents a group which is linked to the mother nucleus and is selected from C₃-C₃₀The heterocyclic aryl group of (a);

Y₁-Y₈selected from C or N; x is selected from O, S, NR or CR 'R';

r, R 'and R' are each independently selected from C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

ar is selected from substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

R¹、R²and R³Each independently selected from H, C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of heterocyclic aryl; r¹、R²And R³Each independently can be connected with the connected mother core structure to form a ring;

m and n are independently selected from integers of 0-4, and p is selected from integers of 0-2.

In particular, when m is 2, 3 or 4, any two adjacent R are¹May together form a ring structure with the carbon atoms to which they are bonded; when n is 2, 3 or 4, any two adjacent R²May together form a ring structure with the carbon atoms to which they are bonded; when p is 2, 3 or 4, any two adjacent R³May together form a ring structure together with the carbon atom to which they are bonded, and the above-formed ring structure may be a cycloalkyl structure, an aryl structure or a heteroaryl structure.

Specifically, when the substituent exists in the groups, the substituent groups are respectively and independently selected from halogen and C₁-C₁₀Alkyl or cycloalkyl of, C₂-C₁₀Alkenyl radical, C₁-C₆Alkoxy or thioalkoxy group of (C)₆-C₃₀Monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon group of (A), C₃-C₃₀The monocyclic heteroaromatic group or the condensed ring heteroaromatic group of (a).

In particular, when defining the above R¹、R²、R³And Ar, when each independently selected from aryl, is an aromatic ring system having a certain number of ring backbone carbon atoms, including monocyclic ring structure substituents such as phenyl and the like, as well as aromatic ring substituents of covalently linked structures such as biphenyl, terphenyl and the like.

In particular, when defining the above R¹、R²、R³And A, Ar, each independently selected from heterocyclic aryl groups, refers to a monocyclic or fused ring aryl group containing one or more heteroatoms selected from B, N, O, S, P (═ O), Si, and P, and having ring carbon atoms.

Further, A in the formula (1) is preferably one of the following chemical formulae (2-1) to (2-5):

wherein, Y₉-Y₃₆Selected from CR 'or N, R' being as defined in formula (1);

still further, wherein: y is₉-Y₁₄At least one of them is N, Y₁₅-Y₂₀At least one of them is N, Y₂₁-Y₂₈At least one of them is N, Y₂₉-Y₃₆At least one of which is N;

indicates the position of the bond.

Still further, the formula (1) is preferably a structural compound of the following formulae (3-1) to (3-2):

in the formulae (3-1) and (3-2): y is₁-Y₈、X、Ar、R¹、R²、R³And m, n and p are each as defined in the general formula (1).

Still more preferably, in the above general formula (1), general formula (3-1) and general formula (3-2), Y₅-Y₈At least one of them is N, Y₁-Y₄At least one of which is N.

Still further, in the general formula (1), the general formula (3-1) and the general formula (3-2), Ar is preferably one group selected from phenyl, biphenyl, terphenyl, naphthyl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, carbazolyl, azacarbazolyl, anthracenyl and fluoranthenyl.

Further, in the general formula (1) of the present invention, the following compounds having specific structures can be preferably selected: A1-A71, these compounds being representative only.

The invention also provides, as another aspect thereof, the use of a compound as described above in an organic electroluminescent device. The compounds of the invention are preferably used as light-emitting host materials in organic electroluminescent devices.

As still another aspect of the present invention, the present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode, and a plurality of organic layers interposed between the first electrode and the second electrode, the organic layers containing a compound represented by the following general formula (1):

in formula (1):

a represents a group which is linked to the mother nucleus and is selected from C₃-C₃₀The heterocyclic aryl group of (a);

Y₁-Y₈selected from C or N; x is selected from O, S, NR or CR 'R';

r, R 'and R' are each independently selected from C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

ar is selected from substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of the heterocyclic aryl groups of (a);

R¹、R²and R³Each independently selected from H, C₁-C₁₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C₃-C₃₀One of heterocyclic aryl; r¹、R²And R³Each independently can be connected with the connected mother core structure to form a ring;

m and n are independently selected from integers of 0-4, and p is selected from integers of 0-2. In particular, when m is 2, 3 or 4, any two adjacent R are¹May together form a ring structure with the carbon atoms to which they are bonded; when n is 2, 3 or 4, any two adjacent R²May together form a ring structure with the carbon atoms to which they are bonded; when p is 2, 3 or 4, any two adjacent R³May together form a ring structure together with the carbon atom to which they are bonded, and the above-formed ring structure may be a cycloalkyl structure, an aryl structure or a heteroaryl structure.

Specifically, when the above-mentioned group has a substituent, the substituent isAre independently selected from halogen, C₁-C₁₀Alkyl or cycloalkyl of, C₂-C₁₀Alkenyl radical, C₁-C₆Alkoxy or thioalkoxy group of (C)₆-C₃₀Monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon group of (A), C₃-C₃₀The monocyclic heteroaromatic group or the condensed ring heteroaromatic group of (a).

Further, the compound of the general formula (1) contained in the organic layer in the above-described organic electroluminescent device of the present invention may preferably be a structural compound of the following formulae (3-1) to (3-2):

in the formulae (3-1) and (3-2): y is₁-Y₈、X、Ar、R¹、R²、R³And m, n and p are each as defined in the general formula (1).

Researches show that the compound with the general formula has good film-forming property and is suitable for being used as a luminescent main body material. The principle is not clear, and it is assumed that the following reasons may be:

the compound of the general formula has a parent structure of a condensed aromatic ring with azapolycyclic conjugated characteristics, and has high bond energy among atoms and good thermal stability; the solid state accumulation among molecules is facilitated, and the service life of the material is prolonged; the aza-condensed ring has higher triplet state energy level, is beneficial to the transition of excitons of the light emitting layer to dyes, and improves the light emitting efficiency.

Due to the existence of the large conjugated segment, the fused heterocyclic compound can effectively improve the HOMO value, is beneficial to injecting holes, improves the hole injection efficiency and realizes a good voltage reduction effect. The large conjugated system enables the transfer of charges in the system to be more effective, and the transition rate of the charges is improved. When the fragment of the fused heterocycle is connected with the electron-absorbing group, the free transmission of electrons in molecules is realized, and the exciton utilization rate can be improved in the application of the luminescent layer main body; when the substituent group of the fused heterocyclic segment is changed into the power supply group, the fused heterocyclic segment can be used as a cavity type material and used as a double-host material to be applied to a device, and the luminous efficiency can be improved.

In particular, the compound of formula (1) may be used as a light emitting layer material in an organic electroluminescent device, but is not limited thereto.

In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.

Detailed Description

The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.

Compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. Solvents and reagents used in the present invention, such as methylene chloride, petroleum ether, ethanol, tetrahydrofuran, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and the like, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Bidi medicine, carbofuran, and the like. In addition, they can be synthesized by a known method by those skilled in the art.

The analytical testing of intermediates and compounds in the present invention uses an abciex mass spectrometer (4000QTRAP) and a siemens analyzer.

The synthesis of the compounds of the present invention is briefly described below.

Representative synthetic route:

by replacing different substrates₂Different target compounds can be obtained. The above synthesis method uses C-N and C-C coupling, but is not limited to this coupling method, and those skilled in the art may select other methods, but is not limited to these methods, and may select them as needed.

More specifically, the following gives synthetic methods of representative compounds of the present invention.

Synthesis example 1: synthesis of Compound A1

In a reaction flask, 17.8g (100mmol) of 3-chloro-2-aminoquinoline and 26.3g (100mmol) of 4-bromo-dibenzothiophene were added,

pd2(dba)30.9g (0.785mmol, 0.5%), tri-tert-butylphosphine 2ml, toluene 1500ml, sodium tert-butoxide 43.3g (314mmol), reaction at 100 ℃ for 8 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, washing with water, concentrating the organic phase, and performing column chromatography to obtain M1.

N₂Protection, adding 36g (100mmol) of M1, adding Pd (OAc) (2mmol), tricyclohexylphosphine (2mmol), potassium carbonate 43.3g (314mmol) and 1000ml of DME, heating and refluxing for 12h, after the reaction is finished, evaporating the solvent, and performing silica gel column chromatography to obtain an M2 intermediate.

Into a reaction flask were charged M232.4g (100mmol), 16.5g (110mmol) of 2-chloro-4, 6-diphenyltriazine, 30.9g (0.785mmol, 0.5%) of Pd2(dba), 1500ml of toluene, 43.3g (314mmol) of potassium carbonate, and reacted at 100 ℃ for 3.5 hours. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered and the resulting solid purified by recrystallization from toluene to give a 1.

¹H NMR(CDCl3,400MHz)8.67(s,1H),8.45(s,1H),8.36(s,2H),8.12(s,2H),7.86(s,1H),7.80(s,1H),7.75(d,J＝12.0Hz,2H),7.63–7.47(m,8H),7.32(d,J＝8.0Hz,2H).

Synthesis example 2:

to a reaction flask were added 25.2g (100mmol) of 6-nitro-7-bromoquinoline, 28.7g (100mmol) of 1-boronic acid-N-phenylcarbazole, 40.9g (0.785mmol, 0.5%) of Pd (Pph3), 1500ml of toluene, 500ml of ethanol, 500ml of water, 43.3g (314mmol) of potassium carbonate, and reacted at 80 ℃ for 8 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, washing with water, concentrating the organic phase, and performing column chromatography to obtain M1.

N₂Protection, adding 41.5g (100mmol) of M1, adding triphenylphosphine (100mmol) and 1000ml o-dichlorobenzene, heating and refluxing, and reactingAnd after the reaction is finished, evaporating the solvent, and performing silica gel column chromatography to obtain an M2 intermediate.

To a reaction flask were added M238.3g (100mmol), 20g (110mmol) of 2-bromonaphthalene, 30.9g (0.785mmol, 0.5%) of Pd2(dba), tri-tert-butylphosphine (5ml), 1500ml of toluene, 43.3g (314mmol) of potassium carbonate, and reacted at 100 ℃ for 3.5 hours. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered and the resulting solid purified by recrystallization from toluene to give a 18.

¹H NMR(CDCl3,400MHz)8.90(s,1H),8.55(s,1H),8.39(s,1H),8.21(s,1H),8.10(s,1H),8.03(s,3H),7.83(s,1H),7.57(m,9H),7.38(d,J＝12.0Hz,2H),7.13(d,J＝10.0Hz,2H),7.00(s,1H).

Synthesis example 3:

in a reaction flask, 25.2g (100mmol) of 7-nitro-8-bromoquinoline, 28.7g (100mmol) of 1-boronic acid-N-phenylcarbazole, 40.9g (0.785mmol, 0.5%) of Pd (Pph3), 1500ml of toluene, 500ml of ethanol, 500ml of water, 43.3g (314mmol) of potassium carbonate were added, and the mixture was reacted at 80 ℃ for 8 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, washing with water, concentrating the organic phase, and performing column chromatography to obtain M1.

N₂And (3) protecting, adding 41.5g (100mmol) of M1, adding triphenylphosphine (100mmol) and 1000ml of o-dichlorobenzene, heating and refluxing, reacting for 12 hours, evaporating the solvent after the reaction is finished, and performing silica gel column chromatography to obtain an M2 intermediate.

To a reaction flask, M238.3g (100mmol), 20g (110mmol) of 2-chloro-4-phenylquinazoline, 30.9g (0.785mmol, 0.5%) of Pd2(dba), tri-tert-butylphosphine (5ml), 1500ml of toluene, 43.3g (314mmol) of potassium carbonate were added and reacted at 100 ℃ for 3.5 hours. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered and the resulting solid purified by recrystallization from toluene to give a 59.

¹H NMR(CDCl3,400MHz)8.80(s,1H),8.55(s,1H),8.45(s,1H),8.13(s,1H),8.08(d,J＝8.4Hz,2H),8.26–7.74(m,6H),8.26–7.19(m,19H),7.19–6.89(m,3H).

Device embodiments