一种化合物及其应用

Compound and application thereof

文档序号：2558 发布日期：2021-09-17 浏览：55次中文

1. A compound of the general formula having the structure shown in formula (1):

in the formula (1), X is O or S;

ar is selected from one of substituted or unsubstituted C5-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;

the L is selected from one of single bond, substituted or unsubstituted C5-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene;

and in formula (1), when X is O, the-L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl;

the ring A represents a substituent group which is connected with a six-membered ring structure consisting of X and P in a fused manner, and the ring A is selected from one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; preferably, ring A is selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

when the substituent group exists in the groups, the substituent group is selected from one or a combination of at least two of halogen, cyano, carbonyl, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkenyl of C2-C10, alkoxy or thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or condensed ring aryl of C6-C30, monocyclic heteroaryl or condensed ring heteroaryl of C3-C30.

2. The compound according to claim 1, in the formula (1):

ar is selected from one of substituted or unsubstituted C5-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;

l is selected from one of single bond, substituted or unsubstituted C5-C30 arylene, and substituted or unsubstituted C3-C30 heteroarylene.

3. The compound of claim 1, having a structure represented by formula (1-a) or (1-B):

in formulae (1-A) and (1-B), the definition of ring A, L and Ar are the same as in formula (1);

in the formula (1-A), the-L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl.

4. The compound of claim 1, having a structure represented by formula (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), or (1-8):

in formulae (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) and (1-8), the ring A is as defined in formula (1);

in the formula (1-1), L is₁One selected from a substituted or unsubstituted C3-C60 heteroarylene group, a substituted or unsubstituted C5-C60 arylene group, and said-L-Ar is not selected from phenyl, biphenyl, or cyano-substituted phenyl; preferably, L₁One selected from a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C5-C30 arylene group, and said-L-Ar is not selected from phenyl, biphenyl, or cyano-substituted phenyl;

in the formula (1-2), L is₂One selected from single bond, substituted or unsubstituted C3-C60 heteroarylene, and substituted or unsubstituted C5-C60 arylene, preferably, L₂One selected from a single bond, a substituted or unsubstituted C3-C30 heteroarylene group, and a substituted or unsubstituted C5-C30 arylene group;

in the formula (1-2), the Y¹、Y²、Y³、Y⁴And Y⁵Each independently selected from CR₁Or N, and Y¹-Y⁵At least one of them is N, R₁Independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups₁Can be fused into a ring;

in the formula (1-3), L is₃One selected from single bond, substituted or unsubstituted C3-C60 heteroarylene, and substituted or unsubstituted C5-C60 arylene, preferably, L₃One selected from a single bond, a substituted or unsubstituted C3-C30 heteroarylene group, and a substituted or unsubstituted C5-C30 arylene group;

in the formula (1-3), the Z¹、Z²、Z³And Z⁴Each independently selected from CR₂Or N, R₂Independently selected from hydrogen, substituted or unsubstituted C1-C12 chainOne of a cyclic alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C1-C12 chain alkoxy group, a halogen group, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted C1-C12 silyl group, an amino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C3-C30 heteroarylamino group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, and two adjacent R groups₂Can be fused into a ring;

in the formula (1-4), L is₄One selected from substituted or unsubstituted arylene group having C6-C60, and substituted or unsubstituted heteroarylene group having C3-C60, preferably, L₄One selected from the group consisting of substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted C3-C30 heteroarylene;

in the formula (1-4), R is selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, and when R is multiple, adjacent R can be connected in a condensed mode; n is an integer of 1 to 5; and when L is₄When the aryl is C6 arylene, R is not selected from H;

in the formula (1-5), L is₅One selected from a substituted or unsubstituted C3-C60 heteroarylene group, a substituted or unsubstituted C5-C60 arylene group; preferably, L₅One selected from a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C5-C30 arylene group;

in the formula (1-6), L is₆One selected from single bond, substituted or unsubstituted C3-C60 heteroarylene, and substituted or unsubstituted C5-C60 arylene, preferably, L₆One selected from a single bond, a substituted or unsubstituted C3-C30 heteroarylene group, and a substituted or unsubstituted C6-C30 arylene group;

in the formula (1-6), the Y⁶、Y⁷、Y⁸、Y⁹And Y¹⁰Each independently selected fromCR₃Or N, and Y⁶-Y¹⁰At least one of them is N, R₃Independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups₃Can be fused into a ring;

in the formula (1-7), L is₇One selected from single bond, substituted or unsubstituted C3-C60 heteroarylene, and substituted or unsubstituted C5-C60 arylene, preferably, L₇One selected from a single bond, a substituted or unsubstituted C3-C30 heteroarylene group, and a substituted or unsubstituted C5-C30 arylene group;

in the formula (1-7), the Z⁵、Z⁶、Z⁷And Z⁸Each independently selected from CR₄Or N, R₄Independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups₂Can be fused into a ring;

in the formula (1-8), L is₈One selected from substituted or unsubstituted arylene group having C6-C60, and substituted or unsubstituted heteroarylene group having C3-C60, preferably, L₈One selected from the group consisting of substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted C3-C30 heteroarylene;

in the formula (1-8), R ' is selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, and when a plurality of R's exist, adjacent R's can be connected in a condensed manner; n' is an integer of 0 to 5;

5. The compound of any one of claims 1-4, wherein ring A is selected from the group consisting of substituted or unsubstituted:

6. The compound of claim 1, having the structure shown below:

7. use of a compound according to any one of claims 1 to 6 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;

preferably, the compound is used as an electron transport material in an organic electroluminescent device.

8. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain the compound according to any one of claims 1 to 6;

preferably, the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is arranged between the hole transport region and the electron transport region; wherein the electron transport region comprises an electron transport layer containing the compound of any one of claims 1 to 6.

Background

Organic Light Emission Diodes (OLED) devices are a kind of devices with sandwich-like structure, which includes positive and negative electrode films and Organic functional material layers sandwiched between the electrode films. And applying voltage to the electrodes of the OLED device, injecting positive charges from the positive electrode and injecting negative charges from the negative electrode, and transferring the positive charges and the negative charges in the organic layer under the action of an electric field to meet for composite luminescence. Because the OLED device has the advantages of high brightness, fast response, wide viewing angle, simple process, flexibility and the like, the OLED device is concerned in the field of novel display technology and novel illumination technology. At present, the technology is widely applied to display panels of products such as novel lighting lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with fast development and high technical requirements.

With the continuous advance of OLEDs in both lighting and display areas, much attention has been paid to the research on their core materials. This is because an efficient, long-lived OLED device is generally the result of an optimized configuration of the device structure and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures. 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.

The OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life is prepared, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device are required to be innovated, and the photoelectric functional material in the OLED device is required to be continuously researched and innovated, so that the functional material with higher performance is prepared. Based on this, the OLED material industry has been working on developing new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better lifetime of the device.

In order to further satisfy the continuously increasing demand for the photoelectric properties of OLED devices and the energy saving demand of mobile electronic devices, new and efficient OLED materials need to be continuously developed, wherein the development of new electron transport materials with high electron injection capability and high mobility is of great significance.

Disclosure of Invention

The object of the present invention is to provide a compound having a higher electron injection ability and a higher electron mobility.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a compound, which has a structure shown in a formula (1);

in the formula (1), X is O or S;

ar is selected from one of substituted or unsubstituted C5-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; preferably, Ar is selected from one of substituted or unsubstituted C5-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;

the L is selected from one of single bond, substituted or unsubstituted C5-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene; preferably, L is selected from one of single bond, substituted or unsubstituted C5-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;

and in formula (1), when X is O, the-L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl;

Further preferably, the compound represented by the formula (1) of the present invention has a structure represented by the following formula (1-A) or (1-B):

in formulae (1-A) and (1-B), the definition of ring A, L and Ar are the same as in formula (1);

in the formula (1-A), the-L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl.

Further preferably, the compound represented by formula (1) of the present invention has a structure represented by the following formula (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) or (1-8):

in formulae (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) and (1-8), the ring A is as defined in formula (1);

in the formula (1-2), the Y¹、Y²、Y³、Y⁴And Y⁵Each independently selected from CR₁Or N, and Y¹-Y⁵At least one of them is N, R₁Independently selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, amino,one of hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, and two adjacent R₁Can be fused into a ring;

in the formula (1-3), the Z¹、Z²、Z³And Z⁴Each independently selected from CR₂Or N, R₂Independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups₂Can be fused into a ring;

in the formula (1-4), R is selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, when R is a plurality of R, adjacent R can be connected through fusion(ii) a n is an integer of 1 to 5; and when L is₄When the aryl is C6 arylene, R is not selected from H;

in the formula (1-6), the Y⁶、Y⁷、Y⁸、Y⁹And Y¹⁰Each independently selected from CR₃Or N, and Y⁶-Y¹⁰At least one of them is N, R₃Independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups₃Can be fused into a ring;

in the formula (1-7), the Z⁵、Z⁶、Z⁷And Z⁸Each independently selected from CR₄Or N, R₄Independently selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy,Halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, wherein two adjacent R groups are₂Can be fused into a ring;

in the formula (1-8), R 'is selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, and when R is multiple, adjacent R's can be connected in a condensed mode; n' is an integer of 0 to 5;

Still further preferably, in said formulae (1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) and (1-8), ring a is selected from the following substituted or unsubstituted substituent groups:

Still more preferably, R is as defined above₁、R₂、R₃、R₄R, R' are each independently selected from hydrogen or the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, grottoyl, perylenyl, anthrylenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenylenyl, trimeric indenyl, isotridecylinyl, trimeric spiroindenyl, spiromesityl, spiroisotridecylinyl, furanyl, isobenzofuranyl, phenyl, terphenyl, anthryl, terphenyl, pyrenyl, terphenyl, etc., p-o, etc Dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, pyrimidyl, benzopyrimidinyl, quinoxalyl, 1, 5-diazaanthracenyl, 2, 7-diazepenyl, 2, 3-diazepenyl, 1, 6-diazepenyl, 1, 8-diazepenyl, 4,5,9, 10-tetraazaOne of an cinnamyl group, a pyrazinyl group, a phenazinyl group, a phenothiazinyl group, a naphthyridinyl group, an azacarbazolyl group, a benzocarbazinyl group, a phenanthrolinyl group, a 1,2, 3-triazolyl group, a 1,2, 4-triazolyl group, a benzotriazolyl group, a 1,2, 3-oxadiazolyl group, a 1,2, 4-oxadiazolyl group, a 1,2, 3-thiadiazolyl group, a 1,2, 4-thiadiazolyl group, a 1,2, 5-thiadiazolyl group, a 1,3, 4-thiadiazolyl group, a 1,3, 5-triazinyl group, a 1,2, 4-triazinyl group, a tetrazolyl group, a 1,2,4, 5-tetrazinyl group, a 1,2,3, 4-tetrazinyl group, a 1,2,3, 5-tetrazinyl group, a purinyl group, a pteridinyl group, an indolizinyl group, and a benzothiadiazolyl group, or a combination selected from the two above.

Further, the compounds described by the general formula of the present invention may preferably be compounds of the following specific structures, which are merely representative:

as another aspect of the present invention, there is also provided a use of the compound as described above in an organic electroluminescent device. In particular, the use as an electron transport layer material in organic electroluminescent devices is preferred.

As still another aspect of the present invention, there is also provided an organic electroluminescent device comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layer contains the compound of the general formula of the present invention represented by any one of the above formulas (1), (1-a), (1-B), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8), or contains the compound represented by each of the specific structural formulae as described above.

Specifically, one embodiment of the present invention provides an organic electroluminescent device including a substrate, and a first electrode, a plurality of light-emitting functional layers, and a second electrode sequentially formed on the substrate; the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, wherein the hole injection transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is arranged between the hole transport region and the electron transport region; wherein, the electron transport region comprises an electron transport layer, and the electron transport layer contains the compound of the general formula shown in any one of the formulas (1), (1-A), (1-B), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) and (1-8) or contains the compound shown in each specific structural formula.

The OLED device prepared by the compound has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel manufacturing enterprises on high-performance materials.

Specifically, one embodiment of the present invention provides an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; wherein the electron transport layer contains the compound of the general formula of the present invention represented by the above formula (1).

More specifically, the organic electroluminescent device will be described in detail.

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).

The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic 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 shown below in HT-1 to HT-34; 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 to 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 to 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 a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, the combination of one or more of BFH-1 through BFH-17 listed below.

In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent dopant may be selected from, but is not limited to, combinations of one or more of BFD-1 through BFD-12 listed below.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more 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.

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 YPD-1 to YPD-11 listed below.

The organic electroluminescent device of the present invention includes 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).

The electron transport region may also be formed using the compound of the present invention for a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL), although the material of the electron transport region may also be combined with one or more 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。

the specific reason why the above-mentioned compound of the present invention is excellent in performance is not clear, and it is presumed that the following reasons may be:

the general formula compound of the invention adopts a novel compound constructed by a novel phosphorus-oxygen electron-deficient group bridged with an electron-deficient group through an aryl or heteroaryl group, and compared with the common structures of single oxazole, thiazole, imidazole, triazole or triazine in the prior art, the structure of the compound of the invention has relatively stronger electron-deficient property, thereby being beneficial to the injection of electrons. Meanwhile, the molecular structure of the compound has larger plane conjugation, thereby being beneficial to improving the mobility of electrons. The structural characteristics of the two aspects can make the molecule show good electron injection and migration performance. Therefore, when the compound is used as an electron transport layer material in an organic electroluminescent device, the electron injection and migration efficiency in the device can be effectively improved, so that the excellent effects of high luminous efficiency and low starting voltage of the device are ensured.

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 specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples. The method and materials for obtaining the compound are not limited to the synthetic methods and materials used in the invention, and other methods or routes can be selected by those skilled in the art to obtain the novel compound provided by the invention. The compounds of the present invention, for which no synthetic method is mentioned, are commercially available starting products or are prepared by the starting products according to known methods.

The basic chemical materials used in the following synthesis examples, such as ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, potassium carbonate, were purchased from Shanghai Tantake technology Co., Ltd and Xiong chemical Co., Ltd. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).

The synthetic route of the compound shown by the general formula of the invention is as follows:

firstly, carrying out substitution reaction on a 1-bromo-2-iodoaryl or heteroaryl compound M-1 and diphenylphosphorus under the catalytic action of Pd (PPh3)4 to generate an intermediate M-2; heating the intermediate M-2 and bromoacetophenone compound M-3 in a toluene solvent to react to generate an intermediate M-4; thirdly, connecting the reaction with the previous step, adding potassium tert-butoxide into the reaction system, and reacting at room temperature for 1 hour to generate a corresponding phosphorus ylide intermediate M-5; fourthly, the reaction of the third step is carried out, Pd (PPh3)4 is added into the reaction system for catalysis, and the reaction is heated and refluxed in toluene for 4 hours to generate an intermediate M-6; fifthly, reacting the intermediate M-6 under the action of NaOH to generate an intermediate M-7; sixthly, reacting the intermediate M-7 with pinacol ester diboron to generate an intermediate M-8; and in the seventh step, the intermediate M-8 and various aryl heteroaryl halides react through Suzuki coupling reaction to generate a final product Cx.

Synthesis example 1:

synthesis of Compound C1

(1) Preparation of Compound 1-1

In a flask, o-iodobromobenzene (310g, 1.1mol), diphenylphosphine (185g, 1mol) and triethylamine (121g, 1.2mol) were dissolved in 1.5L of acetonitrile, and after replacement of nitrogen, Pd (PPh3)4(11.5g, 10mmol) was added. After the addition, the nitrogen was replaced three times and the reaction was heated under reflux with stirring for 6 hours, and the reaction was completed by TLC. Cooling to room temperature, adding water into the reaction system to quench the reaction, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, and purifying by column chromatography to obtain compound 1-1(309g, 91%).

(2) Preparation of Compounds 1-4

Compound 1-1(306g, 0.9mol), 4-chloro-bromoacetophenone (232g, 1mol) was charged into a flask containing 5L of toluene, nitrogen was replaced three times and heated to 90 ℃ with stirring to react for 3 hours to give intermediate compound 1-2. The reaction was allowed to cool to room temperature and potassium tert-butoxide (168g, 1.5mol) was added and the reaction was continued with stirring for 1 hour to afford intermediate compound 1-3. Pd (PPh3)4(57.5g, 50mmol) was added to the reaction system, and after the addition was completed, the reaction was refluxed for 4 hours under nitrogen atmosphere to precipitate a solid, and the reaction was completed by TLC. The temperature was reduced to room temperature, the toluene solvent was removed by rotary evaporation under reduced pressure, water and methylene chloride were added, the mixture was separated, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was washed with toluene and petroleum ether to give compounds 1 to 4(381g, 86%).

(3) Preparation of Compounds 1-5

Dissolving the compound 1-4(369g, 750mmol) in a flask containing 7.5L of dichloromethane, cooling to-10 ℃, keeping the temperature at-10 ℃ to 0 ℃, dropwise adding NaOH (10M, 450ml), and adding 750ml of water after the reaction is finished for 30 minutes. The layers were separated and the aqueous phase was extracted 2 times with dichloromethane, the dichloromethane phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compounds 1-5(211g, 80%).

(4) Preparation of Compounds 1-6

Compound 1-5(176g, 500mmol), pinacol diboron (190g, 750mmol) and potassium acetate (147g, 1.5mol) were charged into a flask containing 1, 4-dioxane (3L), and after replacing nitrogen with stirring at room temperature, palladium acetate (2.24mg, 10mmol) and SPhos (8.2g, 20mmol) were added. After the addition was complete, the reaction was refluxed with stirring for 12 hours, and the end of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, the mixture was separated with water and dichloromethane, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compounds 1 to 6(200g, yield 90%).

(5) Preparation of Compound C1

Compounds 1-6(8.0g, 18mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.8g, 18mmol), potassium carbonate (7.45g, 54mmol), pd (dppf) Cl₂(132mg, 0.18mmol) was added to a flask containing 100mL tetrahydrofuran and 25mL water, the nitrogen was replaced and the reaction was heated to reflux under nitrogen for 10 hours and TLC indicated completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to give compound C1(8.5g, yield 86%). Calculated molecular weight: 549.16, found C/Z: 549.2.

synthesis example 2:

synthesis of Compound C16

The compound C16 was synthesized by a method similar to that of the compound C1, except that the raw material o-iodobromobenzene was replaced by 1-bromo-2-iodonaphthalene, and the raw material 4-chlorobromoacetophenone was replaced by 3-chlorobromoacetophenone. Calculated molecular weight of the resulting compound C16: 599.18, found C/Z: 599.2.

synthetic example 3:

synthesis of Compound C33

The compound C33 was synthesized in a similar manner to the compound C1 except that the starting material o-iodobromobenzene was replaced by 1-bromo-2-iodothiophene and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine was replaced by 2-chloro-4-phenylquinazoline. Calculated molecular weight of the resulting compound C33: 528.11, found C/Z: 528.1.

synthetic example 4:

synthesis of Compound C75

(1) Preparation of Compounds 4-6

The synthesis of the compounds 4-6 adopts a method similar to that of the compounds 1-6, except that the raw material 4-chlorobromoacetophenone is replaced by 5-chloro-2-bromothienylethanone.

(2) Preparation of Compounds 4-7

The compound 2-bromo-5-iodothiophene (28.8g, 100mmol), 4-cyanophenylboronic acid (14.7g, 100mmol), potassium carbonate (41.4g, 300mmol), pd (dppf) Cl₂(732mg, 1mmol) was added to a flask containing 500mL tetrahydrofuran and 100mL water, and the reaction was heated to reflux under nitrogen for 8 hours, TLC showed completion. Cooling to room temperature, separating, extracting water phase with ethyl acetate, mixing organic phases, drying with anhydrous sodium sulfate, filtering, rotary drying under reduced pressure to obtain crude product, separating and purifying by column chromatography to obtain compound 4-7(18.4g,76％)。

(3) preparation of Compound C75

Compound 4-6(8.1g, 18mmol), compound 4-7(2.6g, 18mmol), potassium carbonate (7.45g, 54mmol) was added to a solution containing 1, 4-dioxane: water (150 mL: 50mL) was placed in a flask, nitrogen was replaced at room temperature with stirring, and Pd was added thereto₂(dba)₃(329mg, 0.36mmol), Sphos (295mg, 0.72 mmol). After the addition was complete, the reaction was heated to reflux under nitrogen with stirring for 15 hours and TLC showed completion of the reaction. The precipitated white solid was filtered. Recrystallization after column chromatography gave compound C75 as an off-white solid (7.1g, yield 78%). Calculated molecular weight: 507.05, found C/Z: 507.1.

synthesis example 5:

synthesis of Compound C92

The compound C92 was synthesized by a method similar to that of the compound C1, except that the raw material o-iodobromobenzene was replaced by 3-bromo-4-iodopyridine, and the raw material 4-chlorobromoacetophenone was replaced by 4-chlorobromothioacetophenone. Calculated molecular weight of the resulting compound C92: 566.13, found C/Z: 566.1.

device example 1

The embodiment of the device provides a preparation method of an organic electroluminescent device, which comprises the following steps:

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 until the pressure is less than 10^-5Pa, using a multisource co-evaporation method on the anode layer film, and performing vacuum evaporation on HI-3 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 10 nm;

evaporating HT-4 on the hole injection layer in vacuum to serve as a first hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 40 nm;

evaporating HT-14 on the first hole transport layer in vacuum to serve as a second hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 10 nm;

a luminescent layer of the device is vacuum evaporated on the second hole transport layer, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material BFH-4 is adjusted to be 0.1nm/s, the evaporation rate of the dye BFD-4 is set in a proportion of 5%, and the total film thickness of evaporation is 20nm by using a multi-source co-evaporation method;

vacuum evaporating ET-17 on the luminescent layer to be used as a hole blocking layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 5 nm;

evaporating an electron transport layer on the hole blocking layer by using a multi-source co-evaporation method, adjusting the evaporation rate of the compound C1 to be 0.1nm/s, setting the proportion of the evaporation rate to the evaporation rate of ET-57 to be 100%, and setting the total film thickness of evaporation to be 23 nm;

LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 80nm is used as a cathode of the device.

Device examples 2 to 5 differed from device example 1 only in that the electron transport layer material was replaced with the compound C1 of the present invention by the compounds C16, C33, C75, and C92 of the present invention, respectively, as described in detail in table 1 below.

Comparative device examples 1 to 4

The difference from device example 1 is that the electron transport layer material was replaced by compound C1 of the present invention with compounds D-1, D-2, D-3 and D-4 of the prior art.

And (3) performance testing:

the light emission meters of PR 750 type, ST-86LA type (photoelectric Instrument factory, university of Beijing) and Keithley4200 test system of Photo Research corporation were used to measure the brightness of the light emitted from the light sources of examples 1 to 5 and comparative examples 1 to 4 at the same brightnessDriving voltage and current efficiency of the organic electroluminescent device. 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 1000cd/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 results of the performance tests are shown in table 1 below.

Table 1:

as can be seen from table 1, in the case that the material schemes and the preparation processes of other functional layers in the organic electroluminescent device structure are completely the same, compared with the comparative example, the current efficiency of each organic electroluminescent device prepared in the device examples 1 to 5 of the present invention is higher, and the driving voltage is lower, and in the device examples 1 to 5, the current efficiency of the device is 8.51 to 9.05cd/a, and the driving voltage of the device is 3.89 to 4.05V.

The device prepared in comparative example 1 had a driving voltage of 4.37V and a current efficiency of 8.16 cd/a; the device prepared in comparative example 2 had a driving voltage of 5.16v and a current efficiency of 6.85 cd/A; the device prepared in comparative example 3 had a driving voltage of 5.33v and a current efficiency of 6.47 cd/A; the device prepared in comparative example 4 had a driving voltage of 4.51v and a current efficiency of 7.74 cd/A. The devices prepared in comparative examples 1 to 4 all performed slightly worse than the devices prepared in examples 1 to 5 of the device of the present invention. The reason is presumably that the novel compound constructed by bridging the phosphorus-oxygen electron-deficient group at the 3-position of the phosphorus-oxygen electron-deficient group through the aryl or heteroaryl in the molecular structure has better molecular dipole moment than the comparative example molecule, is favorable for stacking with molecules and further can form a denser molecular film, so that the electron transport capability is stronger. The comparative example D-4 molecule, although containing a similar electron-deficient structure of the present invention, showed relatively poor photoelectric properties due to its low molecular weight and low glass transition temperature, resulting in poor thermal stability of the solid thin film applied to the device.

Experiments prove that the novel compound constructed by bridging the phosphorus-oxygen electron-deficient group at the 3-position through the aryl or heteroaryl and the electron-deficient group in the compound has good electron injection and migration performances when used as an electron transport material, so that a device has high current efficiency and low driving voltage.

The experimental data show that the novel organic material is an organic luminescent functional material with good performance as an electron transport material of an organic electroluminescent device, and has wide application prospect.

The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

完整详细技术资料下载

上一篇：石墨接头机器人自动装卡簧、装栓机

Compound and application thereof

相关技术

网友询问留言