阅读说明：本技术 一种以二苯并环庚烯为核心的化合物及其应用 (Compound with dibenzosuberene as core and application thereof ) 是由 李崇 王芳 张兆超 徐浩杰 于 2018-06-29 设计创作，主要内容包括：本发明公开了一种以二苯并环庚烯为核心的化合物及其应用,属于半导体技术领域。本发明提供的化合物的结构如通式(1)所示：<Image he="407" wi="700" file="DDA0001714582310000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明还公开了上述化合物的应用。本发明的化合物含有二苯并环庚烯结构,具有较高的玻璃化转变温度和分子热稳定性,合适的HOMO和LUMO能级,应用于OLED器件制作后,可有效提高器件的发光效率和OLED器件的使用寿命。(The invention discloses a compound taking dibenzosuberene as a core and application thereof, belonging to the technical field of semiconductors. The structure of the compound provided by the invention is shown as a general formula (1): the invention also discloses application of the compound. The compound contains a dibenzosuberene structure, has higher glass transition temperature and molecular thermal stability and proper HOMO and LUMO energy levels, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.)

1. A dibenzosuberene-based compound is characterized in that the structure of the compound is shown as a general formula (1):

in the general formula (1), Ar is₁、Ar₂、Ar₃、Ar₄Each independently represents a single bond, substituted or unsubstituted C₆-C₃₀One of arylene, 5-to 30-membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur; ar (Ar)₁、Ar₂、Ar₃、Ar₄The same or different;

x represents a single bond, -O-, -S-, -C (R)₉)(R₁₀)-、-N(R₁₁) -or-Si (R)₁₂)(R₁₃)-；

Z is represented by C-R₁₄Or a nitrogen atom; and Z at the bonding site represents a carbon atom;

m, n, p and q are respectively and independently expressed as a number 0 or 1, and m + n + p + q is 1;

the R is₁、R₂、R₃、R₄Respectively independent representationIs a hydrogen atom or a structure represented by the general formula (2);

in the general formula (2), Y represents C-R₁₅Or a nitrogen atom;

said X₁Is represented by a single bond, -O-, -S-, -C (R)₁₆)(R₁₇)-、-N(R₁₈) -or-Si (R)₁₉)(R₂₀)-；

The R is₅、R₆Independently represent a hydrogen atom, a structure represented by general formula (3), general formula (4), general formula (5) or general formula (6); r₅、R₆The same or different; r₅、R₆Not hydrogen at the same time;

in the general formulae (3) and (4), X is₂、X₃、X₄Independently represent-O-, -S-, -C (R)₂₁)(R₂₂)-、-N(R₂₃) -or-Si (R)₂₄)(R₂₅)-；

Said Y is₁Is represented by C-R₂₆Or a nitrogen atom;

general formula (3), general formula (4) and general formula (5) are represented by C_L1-C_L2Key, C_L2-C_L3Key, C_L3-C_L4Key, C_L’1-C_L’2Key, C_L'2-C_L’3Key, C_L’3-C_L’4A bond and a fused ring of formula (2), and Y at the point of attachment represents a carbon atom;

in the general formula (6), R is₇、R₈Each independently represents substituted or unsubstituted C_6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur;

the R is₉-R₁₃、R₁₆-R₂₅Are each independently represented by C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r₉And R₁₀、R₁₂And R₁₃、R₁₆And R₁₇、R₁₉And R₂₀、R₂₁And R₂₂、R₂₄And R₂₅Can be bonded to each other to form a ring;

the R is₁₄、R₁₅Or R₂₆Each independently represents a hydrogen atom, C₁-C₂₀Alkyl, substituted or unsubstituted C_6-C₃₀One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R₁₄、R₁₅Or R₂₆Can be bonded to each other to form a ring;

the substituent is halogen, cyano, C₁-C₁₀Alkyl of (C)₆-C₃₀Aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms; the heteroatom is selected from oxygen, nitrogen or sulfur.

2. The dibenzocycloheptene-based compound of claim 1, wherein Ar is Ar₁、Ar₂、Ar₃、Ar₄Each independently represents a single bond, phenylene, naphthylene, biphenylene, or pyridylene;

the R is₇、R₈Each independently represents one of phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl or anthryl; wherein the hydrogen in the phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl, or anthracenyl group is optionally substituted with a fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, or pyridylSubstituted with one or more of;

the R is₉-R₁₃、R₁₆-R₂₅Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; wherein R is₉And R₁₀、R₁₂And R₁₃、R₁₆And R₁₇、R₁₉And R₂₀、R₂₁And R₂₂、R₂₄And R₂₅Can be bonded to each other to form a ring;

the R is₁₄、R₁₅Or R₂₆Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group; two or more adjacent R₁₄、R₁₅Or R₂₆May be bonded to each other to form a ring.

3. The dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (1) is any one of formulae (i) to (ii):

4. the dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (2) is any one of formulae (1-1) to (1-4):

5. the dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (2) is any one of formulae (1-5) to (1-9):

6. the dibenzosuberene-cored compound of claim 1, wherein the compound has the following structure:

7. An organic electroluminescent device, characterized in that at least one functional layer contains a dibenzocycloheptene-based compound according to any one of claims 1 to 6.

8. An organic electroluminescent device according to claim 7, wherein the functional layer is a light-emitting layer and/or an electron-blocking layer and/or a hole-transporting layer.

9. A lighting or display element comprising the organic electroluminescent device according to claim 7 or 8.

Technical Field

The invention relates to a compound taking dibenzosuberene as a core and application thereof, belonging to the technical field of semiconductors.

Background

The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials sandwiched between different electrode film layers, and various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.

Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will be further extended to large-size application fields such as televisions, however, the performance of the OLED device, such as light emitting efficiency and service life, is yet to be further improved compared with the application requirements of the product. The research on improving the performance of the OLED light emitting device mainly includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the structure and the manufacturing process of the OLED device need to be innovated, but also the photoelectric functional material of the OLED needs to be continuously researched and innovated, so as to create the functional material of the OLED with higher performance. The photoelectric functional materials of the OLED applied to the OLED device can be roughly classified into two types from the use point of view, i.e., charge injection transport materials and light emitting materials, the charge injection transport materials can be further classified into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials include host light emitting materials and doping materials. High performance OLED light emitting devices require that various organic functional materials have good optoelectronic properties, for example, as charge transport materials, good carrier mobility, high glass transition temperature, etc., and host materials of the light emitting layer have good ambipolarity and appropriate HOMO/LUMO energy levels.

The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual requirements of the current OLED display illumination industry, the development of the current OLED material is far behind the requirements of panel manufacturing enterprises, and it is very important to develop higher-performance organic functional materials as a material enterprise.

Disclosure of Invention

One of the objects of the present invention is to provide a dibenzosuberene-based compound. The compound contains a dibenzosuberene structure, has higher glass transition temperature and molecular thermal stability and proper HOMO and LUMO energy levels, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.

The technical scheme for solving the technical problems is as follows:

a dibenzosuberene-based compound is characterized in that the structure of the compound is shown as a general formula (1):

in the general formula (1), Ar is₁、Ar₂、Ar₃、Ar₄Each independently represents a single bond, substituted or unsubstituted C₆-C₃₀One of arylene, 5-to 30-membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur; ar (Ar)₁、Ar₂、Ar₃、Ar₄The same or different;

x represents a single bond, -O-, -S-, -C (R)₉)(R₁₀)-、-N(R₁₁) -or-Si (R)₁₂)(R₁₃)-；

Z is represented by C-R₁₄Or a nitrogen atom; and Z at the bonding site represents a carbon atom;

m, n, p and q are respectively and independently expressed as a number 0 or 1, and m + n + p + q is 1;

the R is₁、R₂、R₃、R₄Each independently represents a hydrogen atom or a structure represented by the general formula (2);

in the general formula (2), Y represents C-R₁₅Or a nitrogen atom;

said X₁Is represented by a single bond, -O-, -S-, -C (R)₁₆)(R₁₇)-、-N(R₁₈) -or-Si (R)₁₉)(R₂₀)-；

The R is₅、R₆Independently represent a hydrogen atom, a structure represented by general formula (3), general formula (4), general formula (5) or general formula (6); r₅、R₆The same or different; r₅、R₆Not hydrogen at the same time;

in the general formulae (3) and (4), X is₂、X₃、X₄Independently represent-O-, -S-, -C (R)₂₁)(R₂₂)-、-N(R₂₃) -or-Si (R)₂₄)(R₂₅)-；

Said Y is₁Is represented by C-R₂₆Or a nitrogen atom;

general formula (3), general formula (4) and general formula (5) are represented by C_L1-C_L2Key, C_L2-C_L3Key, C_L3-C_L4Key, C_L’1-C_L’2Key, C_L'2-C_L’3Key, C_L’3-C_L’4A bond and a fused ring of formula (2), and Y at the point of attachment represents a carbon atom;

in the general formula (6), R is₇、R₈Each independently represents substituted or unsubstituted C_6-30Aryl, substituted or not with one or more hetero atomsOne of substituted 5-30 membered heteroaryl; the heteroatom is nitrogen, oxygen or sulfur;

the R is₉-R₁₃、R₁₆-R₂₅Are each independently represented by C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r₉And R₁₀、R₁₂And R₁₃、R₁₆And R₁₇、R₁₉And R₂₀、R₂₁And R₂₂、R₂₄And R₂₅Can be bonded to each other to form a ring;

the R is₁₄、R₁₅Or R₂₆Each independently represents a hydrogen atom, C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R₁₄、R₁₅Or R₂₆Can be bonded to each other to form a ring;

the substituent is halogen, cyano, C₁-C₁₀Alkyl of (C)_6--C₃₀Aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms.

Preferred embodiment, said Ar₁、Ar₂、Ar₃、Ar₄Each independently represents a single bond, phenylene, naphthylene, biphenylene, or pyridylene;

the R is₇、R₈Each independently represents one of phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl or anthryl; wherein the hydrogen in the phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl, or anthracenyl group is optionally substituted with a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl groupPentyl, phenyl, naphthyl, biphenyl or pyridyl;

the R is₉-R₁₃、R₁₆-R₂₅Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; wherein R is₉And R₁₀、R₁₂And R₁₃、R₁₆And R₁₇、R₁₉And R₂₀、R₂₁And R₂₂、R₂₄And R₂₅Can be bonded to each other to form a ring;

the R is₁₄、R₁₅Or R₂₆Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group; two or more adjacent R₁₄、R₁₅Or R₂₆May be bonded to each other to form a ring.

Preferably, the structure of the general formula (1) is any one of formulas (i) to (ii):

preferably, the structure of the general formula (2) is any one of formulas (1-1) to (1-4):

preferably, the structure of the general formula (2) is any one of formulas (1-5) to (1-9):

further, the structure of the general formula (1) is any one of T1-T202:

further, R is₁、R₂、R₃、R₄Has a structure of any one of H1-H133:

further, the specific structural formula of the compound is:

one kind of (1).

The second objective of the present invention is to provide an organic electroluminescent device. When the compound is applied to an OLED device, the stability of a film layer formed by the material can be kept, and the service life of the OLED device is prolonged.

The technical scheme for solving the technical problems is as follows: an organic electroluminescent device, at least one functional layer contains the dibenzosuberene-based compound.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the functional layer is a light emitting layer and/or an electron blocking layer and/or a hole transport layer.

It is a further object of the present invention to provide an illumination or display device. After the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.

The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.

The invention has the beneficial effects that:

1. the compound takes dibenzo cycloheptene as a framework and is connected with a carbazole derivative long branched chain structure, because the electron donating capability of branched chain groups is different, the HOMO energy level of the whole structure of the compound can be freely adjusted, and the compound with shallow HOMO energy level can be used as a hole transport layer/electron blocking layer material; the material with deep HOMO energy level can be used as the host material of the hole bias type light-emitting layer.

In addition, the dibenzosuberene group is a bipolar group, and the branched chain is a long-chain structure, so that the symmetry of the molecular structure is destroyed, and the intermolecular aggregation effect is avoided; dibenzosuberene is used as a mother nucleus, so that free rotation of the group is avoided, the rigidity of the central mother nucleus group is enhanced, and a branched chain group of the compound also has very strong rigidity, so that molecules are not easy to aggregate and crystallize, and the compound has good film-forming property, higher glass transition temperature and thermal stability. Therefore, when the compound is applied to an OLED device, the stability of a film layer formed by the material can be kept, and the service life of the OLED device is prolonged.

2. The compound of the invention has high triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.

Drawings

FIG. 1 is a schematic diagram of a device structure to which the compound of the present invention is applied, wherein the components represented by the respective reference numerals are as follows:

1. transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, luminescent layer, 7, hole blocking/electron transport layer, 8, electron injection layer, 9, cathode reflection electrode layer.

Fig. 2 is a graph of efficiency measured at different temperatures for an OLED device of the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

The present invention will be described in detail below with reference to the accompanying drawings and examples.

Taking the synthesis example of intermediate A1:

1) adding 0.05mol of bromobiphenyl and 0.05mol of Mg powder and 60ml of tetrahydrofuran into a 250ml three-neck flask in the atmosphere of introducing nitrogen, heating to 70 ℃, carrying out reflux reaction for 4 hours, and completely reacting to generate a Grignard reagent; adding 0.05mol of 2-bromo-5-dibenzocycloheptenone and 50ml of tetrahydrofuran into a 250ml three-neck flask in the atmosphere of introducing nitrogen, stirring and dissolving, dropwise adding the Grignard reagent, reacting at 60 ℃ for 24 hours to generate a large amount of white precipitate, and finally adding saturated NHCl₄Converting the grignard salt to an alcohol; after the reaction is finished, extracting with diethyl ether, drying and rotary steaming, and mixing petroleum ether: purifying the dichloromethane mixed solvent (3:2) by a silica gel column to obtain solid tertiary alcohol with yellowish color, wherein the HPLC purity is 98.9 percent, and the yield is 85.1 percent;

elemental analysis Structure (molecular formula C)₂₇H₁₉BrO): theoretical value C, 73.81; h, 4.36; br, 18.19; o, 3.64; test values are: c, 73.83; h, 4.34; br, 18.18; and O, 3.65. HPLC-MS: the molecular weight of the material is 439.35, and the measured molecular weight is 439.46.

2) 0.04mol of the tertiary alcohol and 100ml of dichloromethane are mixed with stirring, 8ml of boron trifluoride-diethyl ether complex is added dropwise at room temperature, the reaction is carried out for 30 minutes, 20ml of ethanol and 20ml of water are added for quenching, the reaction is extracted by dichloromethane (20ml × 3), drying and rotary evaporation are carried out, the petroleum ether silica gel column is used for purification, and the reaction product is purified by ethanol: recrystallizing dichloromethane (volume ratio is 1:1) to obtainIntermediate a1, HPLC purity 99.2%, yield 74.3%; elemental analysis Structure (molecular formula C)₂₇H₁₇Br): theoretical value C, 76.97; h, 4.07; br, 18.96; test values are: c, 77.02; h, 4.13; br, 18.99.

HPLC-MS: the molecular weight of the material is 421.34, and the measured molecular weight is 421.37.

Intermediate a was prepared by the synthetic method of intermediate a1, the specific structure is shown in table 1.

TABLE 1