CN113527330B - Compound and application thereof - Google Patents

Compound and application thereof Download PDF

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CN113527330B
CN113527330B CN202010294719.6A CN202010294719A CN113527330B CN 113527330 B CN113527330 B CN 113527330B CN 202010294719 A CN202010294719 A CN 202010294719A CN 113527330 B CN113527330 B CN 113527330B
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CN113527330A (en
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孙恩涛
方仁杰
吴俊宇
刘叔尧
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Beijing Eternal Material Technology Co Ltd
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    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention relates to a compound and application thereof, the compound has a structure shown in a formula (1), the compound takes an electron-deficient large conjugated structure of imidazo nitrogen sulfur (oxygen) heteroseven-membered cycloacene as a mother nucleus and is connected with Ar groups, the compound structure has stronger electron-deficient property, which is beneficial to electron injection, and meanwhile, the electron-deficient group of the large conjugated structure leads molecules to have good plane conjugation, thereby being beneficial to improving electron mobility and leading the whole molecule to show good electron injection and migration performance, therefore, when the compound disclosed by the invention is used as an organic electroluminescent device, especially as an electron transport layer material, the electron injection and migration efficiency in the device can be effectively improved, thereby ensuring that the device obtains excellent effects of high luminous efficiency and low starting voltage.

Description

Compound and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound and application thereof.
Background
An organic electroluminescent (OLED: organic Light Emission Diodes) device is a device with a sandwich-like structure, comprising positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. And applying voltage to the electrode of the OLED device, injecting positive charges from the positive electrode, injecting negative charges from the negative electrode, and transferring and meeting the positive charges and the negative charges in the organic layer to emit light compositely under the action of an electric field. Because the OLED device has the advantages of high brightness, quick response, wide viewing angle, simple process, flexibility and the like, the OLED device has a great deal of attention in the novel display technical field and the novel illumination technical field. At present, the technology is widely applied to display panels of products such as novel illumination 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 rapid development and high technical requirements.
With the continuous advancement of the OLED in the two fields of illumination and display, the research on the core materials of the OLED is also more focused. This is because an efficient, long-life OLED device is typically the result of an optimized match of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functionalized materials of various structures. Common functionalized organic materials are: a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, a light emitting host material, a light emitting guest (dye), and the like.
In order to prepare the OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life of the device, 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 as to prepare the functional material with higher performance. Based on this, the OLED materials community has been striving to develop new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better lifetime of the device.
In order to further meet the demand for the continuous improvement of the photoelectric performance of OLED devices and the demand for energy saving of mobile electronic devices, there is a continuous need to develop new and efficient OLED materials, where the development of new electron transport materials with high electron injection capability and high mobility is of great importance.
Disclosure of Invention
It is an object of the present invention to provide a compound, particularly a compound for an organic electroluminescent device, and more particularly, a compound for an organic electroluminescent device, which has high electron injection ability and electron mobility, can improve current efficiency of the device, and can reduce driving voltage, as an electron transport material for the organic electroluminescent device.
To achieve the purpose, the invention adopts the following technical scheme:
The present invention provides a compound having a structure represented by formula (1);
in the formula (1), X is S or O;
In the formula (1), ar is selected from any one of substituted or unsubstituted C8-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl and cyano;
in the formula (1), L is selected from any one of single bond, substituted or unsubstituted C6-C60 arylene and substituted or unsubstituted C3-C60 heteroarylene;
In formula (1), each of R 1 and R 2 is independently selected from any one of hydrogen, deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
In the formula (1), R is selected from any one of deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
in the formula (1), n is an integer of 0 to 7, for example, 1, 2,3, 4,5, 6, etc., preferably n is 0 or 1, and m is an integer of 0 or 1;
In the formula (1), Y represents a single bond; when m is 0, R 1 and R 2 are two independent substituents which are not connected, when m is 1, R 1 and R 2 are connected through a single bond Y, and when either R 1 or R 2 is selected from hydrogen, deuterium, halogen, cyano or nitro, they cannot be connected according to common general knowledge in the art, i.e. m can only be 0;
Ar, L, R 1、R2 and R, wherein each substituted group is independently selected from one or a combination of at least two of halogen, cyano, nitro, hydroxy, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 fused ring heteroaryl. "monocyclic aryl" refers to aryl groups that do not contain condensed groups, e.g., phenyl, biphenyl, terphenyl, all belong to monocyclic aryl groups, and "condensed aryl" refers to condensed aryl groups, e.g., naphthyl, anthryl, phenanthryl, and the like, monocyclic heteroaryl groups and fused ring heteroaryl groups being the same.
In Ar, L, R 1、R2 and R, the number of the substituted groups is 1 to the maximum substitutable number, the groups listed in the previous paragraph refer to the selection range of the substituent groups when the substituent groups exist on the substituted or unsubstituted groups, one substituent group can be substituted on the substituted or unsubstituted groups, a plurality of substituent groups can be substituted on the substituted or unsubstituted groups, when the substituent groups are a plurality of substituent groups, the substituent groups can be selected from different substituent groups, the same meaning is achieved when the same expression mode is involved in the invention, and the selection range of the substituent groups is not repeated one by one.
In a preferred embodiment of the present invention, each of Ar, L, R 1、R2 and R is independently selected from any one or a combination of at least two of cyano, phenyl, methyl or pyridyl.
In the present invention, the heteroatom of the heteroaryl group is generally selected from N, O, S.
In the present invention, the expression "ring structure" means that the linking site is located at any position on the ring structure that can be bonded.
In the present invention, the carbon number of the C8-C60 aryl group, C6-C60 (arylene) group may be C8, C10, C12, C14, C16, C18, C20, C26, C28, C30, C32, C34, C36, C38, C40, C42, C46, C48, C50, C52, C54, C56, C58, etc.;
In the present invention, the C3-C60 (ene) heteroaryl group may have a carbon number of C4、C5、C6、C7、C8、C10、C12、C14、C16、C18、C20、C26、C28、C30、C32、C34、C36、C38、C40、C42、C46、C48、C50、C52、C54、C56、C58 or the like;
In the invention, the carbon number of the C2-C20 alkenyl, C2-C20 alkynyl and C1-C20 alkyl can be C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18 and the like;
in the present invention, the carbon number of the C3-C21 cycloalkyl group may be C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18, C19, C20, etc.;
in the invention, the carbon number of the C1-C10 chain alkyl, the C1-C10 alkoxy and the C1-C10 thioalkoxy can be C2, C3, C4, C5, C6, C7, C8, C9, C10 and the like;
in the invention, the carbon number of the C3-C10 cycloalkyl can be C4, C5, C6, C7, C8, C9 and the like;
In the present invention, the carbon number of the C6-C30 arylamino group may be C8, C10, C12, C14, C16, C18, C20, C26, C28, etc.;
In the invention, the carbon number of the C3-C30 heteroaryl amino group can be C3, C4, C6, C8, C10, C12, C14, C16, C18, C20, C26, C28 and the like;
in the invention, the carbon number of the C6-C30 monocyclic aryl can be C8, C10, C12, C14, C16, C18, C20, C26, C28 and the like; the carbon number of the C10-C30 condensed ring aryl group can be C12, C14, C16, C18, C20, C26, C28 and the like; the carbon number of the C3-C30 monocyclic heteroaryl can be C3, C4, C6, C8, C10, C12, C14, C16, C18, C20, C26, C28 and the like; the carbon number of the C6-C30 fused ring heteroaryl group can be C8, C10, C12, C14, C16, C18, C20, C26, C28 and the like.
The number of carbons is merely illustrative and is not limited to the above.
The compound provided by the invention adopts imidazo nitrogen sulfur (oxygen) hetero seven-membered cyclodibenzoThe electron-deficient large conjugated structure is a mother nucleus and is connected with Ar groups, the compound structure has stronger electron-deficient property, which is beneficial to electron injection, and meanwhile, the electron-deficient groups of the large conjugated structure lead molecules to have good plane conjugation, thereby being beneficial to improving the mobility of electrons.
The compound has the characteristics that the whole molecule can show good electron injection and migration performance, so when the compound is used in an organic electroluminescent device, particularly used as an electron transport material, the electron injection and migration efficiency in the device can be effectively improved, and 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 easy to implement, raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
Preferably, m is 0, i.e. the structure of formula (1) is as follows:
Ar, L, R 1、R2, R, X and n all have the same meaning as before.
Preferably, the compound has a structure represented by formula (1-1) or formula (1-2);
The Ar, L, R 1、R2, R and n have the same meanings as those in the formula (1).
Preferably, the compound has any one of structures represented by formulas (a) to (h);
Each R 3-R9 is independently selected from any one of hydrogen, deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
In R 3-R9, the substituted groups are each independently selected from one or a combination of at least two of halogen, cyano, nitro, hydroxy, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 fused ring heteroaryl;
Ar, L and R 1、R2 have the same meaning as in formula (1).
The present invention preferably uses an imidazo-aza-seven-membered cycloacene as a parent nucleus (i.e., X is S), which has a higher conjugated electron cloud density than an imidazo-aza-seven-membered cycloacene as a parent nucleus (i.e., X is O), and thus can further improve the current efficiency of the device.
Preferably, ar is selected from any one of substituted or unsubstituted C8-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl and cyano, preferably substituted or unsubstituted C3-C30 electron-deficient heteroaryl or cyano.
The invention preferably replaces electron-deficient group Ar on the imidazo nitrogen sulfur (oxygen) hetero seven-membered cyclodiphenyl nucleus, and can further improve the electron-deficient property of the structure compared with the group without electron-deficient property, thereby being more beneficial to electron injection, further improving the electron injection and migration performance of the compound, and being capable of further improving the luminous efficiency of the device and reducing the driving voltage when being used as an electron transmission material of an organic electroluminescent device.
Compared with the structures such as single oxazole, thiazole, imidazole, triazole or triazine in the prior art, the structure provided by the invention has relatively stronger electron deficiency, so that electron injection is facilitated, and a large conjugated electron deficiency parent nucleus is matched to enable molecules to have good plane conjugation, thereby being beneficial to improving the mobility of electrons and further being beneficial to improving the performance of devices.
In the present invention, the term "electron-deficient heteroaryl" refers to a group having a reduced electron cloud density on an aromatic ring after the group has replaced hydrogen on the aromatic ring, and generally such a group has a Hammett value of more than 0.6. The Hammett value refers to the characterization of the charge affinity for a particular group, and is a measure of the electron withdrawing group (positive Hammett value) or the electron donating group (negative Hammett value). Hammett's equation is described in more detail in Thomas H.Lowry and KatheleenSchueller Richardson, "MECHANISM AND Theory In Organic Chemistry', new York,1987, pages 143-151, which is incorporated herein by reference. Such groups may be exemplified by, but are not limited to: triazinyl, pyrimidinyl, benzopyrimidinyl, benzopyridyl, naphthyridinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, pyridazinyl, and alkyl or aryl substituted radicals as described above. The meaning of the electron-deficient heteroaryl group in the invention is consistent with the electron-deficient group in the text.
Preferably, ar is selected from cyano or any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
Preferably, ar is selected from cyano or any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
Preferably, ar is selected from substituted or unsubstituted triazinyl.
In the invention, ar is preferably a triazine group which has lower electron density, and can be matched with an imidazo nitrogen sulfur (oxygen) hetero-seven-membered cyclodiphenyl nucleus to further improve the electron injection and migration performance; thereby further improving the luminous efficiency of the device and reducing the driving voltage.
Preferably, the L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, preferably a single bond or a substituted or unsubstituted C6-C30 arylene group, further preferably a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted naphthylene group.
Preferably, L is a substituted or unsubstituted phenylene group and Ar is a cyano group.
Preferably, each of R 1 and R 2 is independently selected from any one of hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
Preferably, in R 1 and R 2, the substituted or unsubstituted C6-C30 aryl is cyano-substituted C6-C30 aryl, preferably cyano-substituted phenyl.
It is further preferred in the present invention that R 1 and R 2 are both selected from cyano-substituted aryl groups, and that R 1 and R 2 are joined to the parent nucleus by a single bond such that the overall structure has a symmetrical linear structure, resulting in further improved electron injection and transport efficiency compared to aryl groups not substituted by cyano groups.
Preferably, each of R 1 and R 2 is independently selected from hydrogen or any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
Preferably, each of R 1 and R 2 is independently selected from hydrogen, cyano-substituted phenyl, or any of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
Preferably, the R is selected from a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted C3-C30 heteroaryl, preferably any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
Preferably, each R 3-R9 is independently selected from any one of hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, preferably hydrogen or any one of substituted or unsubstituted:
wherein the wavy line marks represent the bond of the group.
Preferably, the compound has any one of the structures shown in C1 to C75 below:
It is a further object of the present invention to provide the use of a compound according to one of the objects, for use in an organic electronic device.
The organic electronic device comprises an organic electroluminescent device, an optical sensor, a solar cell, an illumination element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet scanner or electronic paper, and preferably an organic electroluminescent device.
Preferably, the compound is used as an electron transport material in the organic electroluminescent device.
It is a further object of the present invention to provide an organic electroluminescent device comprising a substrate, a first electrode, a second electrode and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises at least one compound according to one of the objects.
Preferably, the organic layer comprises an electron transport layer comprising at least one compound of one of the purposes.
Specifically, an 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 transmission layer, a light-emitting layer and an electron transmission layer, wherein the hole injection layer is formed on the anode layer, the hole transmission layer is formed on the hole injection layer, the cathode layer is formed on the electron transmission layer, and the light-emitting layer is arranged between the hole transmission layer and the electron transmission 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 device includes a first electrode and a second electrode, 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 particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. 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 serving as the first electrode on the substrate. When the first electrode is used as the anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), or the like, and any combination thereof may be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and 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 compounds used as the organic material layer may be small organic molecules, large organic molecules and polymers, and combinations 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 hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region may have 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 conductive dopant containing polymers such as polystyrene, 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), and aromatic amine derivatives as 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 of the compounds HT-1 through HT-34 described above, or one or more of the compounds HI-1 through HI-3 described below; one or more compounds of HT-1 through HT-34 may also be used to dope one or more compounds of HI-1 through HI-3 described below.
The luminescent layer comprises luminescent dyes (i.e. dopants) that can emit different wavelength spectra, and may also comprise Host materials (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 plurality of monochromatic light emitting layers with different colors can be arranged in a plane according to the pixel pattern, or can be stacked together 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 simultaneously emitting different colors such as red, green, and blue.
According to different technologies, the luminescent layer material can be made of different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescence luminescent material and the like. In an OLED device, a single light emitting technology may be used, or a combination of different light emitting technologies may be used. The different luminescent materials classified by the technology can emit light of the same color, and can also emit light of different colors.
In one aspect of the invention, the light-emitting layer employs fluorescence electroluminescence technology. The luminescent layer fluorescent host material thereof may be selected from, but is not limited to, one or more combinations of BFH-1 to BFH-17 listed below.
In one aspect of the invention, the light-emitting layer employs fluorescence electroluminescence technology. The luminescent layer fluorescent dopant thereof may be selected from, but is not limited to, one or more combinations of BFD-1 through BFD-12 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescence technology. The luminescent layer host material 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 electroluminescence technology. The luminescent layer phosphorescent dopant thereof may be selected from, but is not limited to, one or more combinations of GPD-1 to GPD-47 listed below.
Wherein D is deuterium.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescence technology. The luminescent layer phosphorescent dopant thereof may be selected from, but is not limited to, one or more combinations of the RPD-1 through RPD-28 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescence technology. The luminescent layer phosphorescent dopant thereof may be selected from, but is not limited to, one or more combinations of YPD-1 through YPD-11 listed below.
The organic electroluminescent device of the present invention includes an electron transport region between a light emitting layer and a 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 by applying the compound of the present invention to a multi-layer 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.
The device may further include an electron injection layer between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following:
Liq、LiF、NaCl、CsF、Li2O、Cs2CO3、BaO、Na、Li、Ca。
compared with the prior art, the invention has the following beneficial effects:
The compound provided by the invention takes the electron-deficient large conjugated structure of imidazo nitrogen sulfur (oxygen) heteroseven-membered cyclodiphenyl as a mother nucleus and is connected with Ar groups, the compound structure has stronger electron-deficient property, is beneficial to electron injection, and meanwhile, the electron-deficient group of the large conjugated structure enables molecules to have good plane conjugation, so that the mobility of electrons is beneficial to improvement. The above-mentioned characteristics can make the molecule as a whole exhibit good electron injection and migration properties, and therefore, when the compound of the present invention is used in an organic electroluminescent device, particularly as an electron transport material, the electron injection and migration efficiency in the device can be effectively improved, thereby ensuring that the device achieves excellent effects of high luminous efficiency and low starting voltage.
In addition, the preparation process of the compound is simple and easy to implement, raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The synthetic route of the compounds shown in the invention is as follows:
The first step of reaction, namely, carrying out aldehyde-amine condensation reaction on substituted o-bromobenzaldehyde and substituted o-diketone in glacial acetic acid solution containing ammonium acetate, and then further closing ring to form an intermediate M1 with an imidazole ring structure; and in the second step, the intermediate M1 and the substituted o-bromophenol or o-bromophenol are subjected to catalytic coupling to obtain the target compound with a seven-membered ring. Wherein X is O or S, R 1、R2, R, N, L and Ar have the same meaning as the general formula (1), NH 4 OAc is ammonium acetate, acOH is glacial acetic acid, O-phen is phenanthroline, and DMF is N, N-dimethylformamide.
The following synthesis examples provide various chemicals used in the synthesis methods of specific compounds, such as ethanol, ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, methylene chloride, 1, 4-dioxane, N-dimethylformamide, potassium carbonate, potassium acetate, cuprous iodide, etc., which were purchased from Shanghai taitan technologies and chemical company of the ridge chemical company. The mass spectrometer used for determining the following compounds was ZAB-HS type mass spectrometer measurement (manufactured by Micromass Co., UK).
Synthesis example 1:
Synthesis of Compound C1
(1) Preparation of Compound 1-1
The compound 2-bromo-4-chlorobenzaldehyde (218 g,1.0 mol) was added to a 5L flask containing 2L glacial acetic acid, and ammonium acetate (154 g,2.0 mol) and diphenyldione (210 g,1.0 mol) were slowly added in portions with stirring at room temperature, and the reaction was stirred at 120℃for 4 hours under reflux after the addition, and TLC monitoring showed completion of the reaction. After the reaction solution was cooled to room temperature, it was slowly poured into 4L of water to precipitate a large amount of solid, and the solid was purified by column chromatography after suction filtration to give Compound 1-1 (381 g, yield 93%).
(2) Preparation of Compounds 1-2
Compound 1-1 (40.8 g,100 mmol), o-bromophenyl thiophenol (18.8 g,100 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after replacing nitrogen, cuprous iodide (0.38 g,2.0 mmol) and phenanthroline (0.79 g,4.0 mol) were added, respectively, nitrogen was replaced 4 times, and the reaction was refluxed with stirring at 110℃for 12 hours, and TLC monitored the reaction end point. After the reaction is cooled to room temperature, slowly pouring the mixture into 2L of cold water to precipitate a large amount of solids, leaching the filtered solids with water and ethanol for three times respectively, drying the solids, and separating and purifying the dried solids by column chromatography to obtain the compound 1-2 (31 g, yield 71%).
(3) Preparation of Compounds 1-3
Compounds 1-2 (30 g,69 mmol), pinacol diboronate (26.3 g,104 mmol), potassium acetate (13.5 g,138 mmol) were added to a 1L flask containing 300mL of 1, 4-dioxane, and palladium acetate (0.35 g,1.38 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (1.13 g,2.76 mmol) were added after displacing nitrogen with stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was stirred at reflux for 12 hours, and TLC monitored the end of the reaction. The 1, 4-dioxane was removed by rotary evaporation, water and methylene chloride were added to the mixture, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 1-3 (32 g, yield 88%).
(4) Preparation of Compound C1
Compounds 1-3 (10 g,19 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.3 g,19 mmol), potassium carbonate (5.4 g,38 mmol) and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) were added to a flask containing 100mL tetrahydrofuran and 25mL water, the nitrogen was replaced and the reaction was heated at reflux for 4 hours under nitrogen, and TLC showed complete reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound C1 (9.6 g, yield 80%). Calculated molecular weight: 633.20, found C/Z:633.2.
Synthesis example 2:
synthesis of Compound C20
(1) Preparation of Compound 2-1
The compound 4,4' -dibromodiacetone (36.6 g,100 mmol), 4-pyridineboronic acid (24.6 g,200 mmol), potassium carbonate (27.6 g,200 mmol), and tetraphenylpalladium phosphate (1.0 g,0.87 mol) were charged into a 2L flask containing 500L toluene, 100mL ethanol, and 100mL water, nitrogen was replaced, and the reaction was heated under reflux under a nitrogen atmosphere for 4 hours, and TLC showed completion of the reaction. Cooling to room temperature, separating, extracting the aqueous phase with ethyl acetate, mixing the organic phases, drying over anhydrous sodium sulfate, and separating and purifying by column chromatography to obtain compound 2-1 (29.2 g, yield 80%).
(2) Preparation of Compound 2-2
Compound 2-1 (29 g,79.7 mmol) was added to a 500mL flask containing 200mL of glacial acetic acid, ammonium acetate (12.3 g,159.4 mmol) was added slowly in portions with stirring at room temperature, and the reaction was stirred at 120℃for 4 hours under reflux, and TLC monitoring showed complete reaction. After the reaction solution was cooled to room temperature, it was slowly poured into 1L of water to precipitate a large amount of solid, and the solid was purified by column chromatography after suction filtration to give Compound 2-2 (40.3 g, yield 90%).
(3) Preparation of Compounds 2-3
Compound 2-2 (40.0 g,71.2 mmol), o-bromophenyl thiophenol (12.2 g,71.2 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after nitrogen substitution, cuprous iodide (0.27 g,1.4 mmol) and phenanthroline (0.56 g,2.8 mol) were added, respectively, nitrogen substitution was performed 4 times, and reflux reaction was stirred at 110℃for 8 hours, and TLC monitored for the end of the reaction. After the reaction is cooled to room temperature, the mixture is slowly poured into 2L of cold water to precipitate a large amount of solid, the solid after suction filtration is respectively leached with water and ethanol for three times, the solid is dried, and the dried solid is separated and purified by column chromatography to obtain the compound 2-3 (26 g, yield 62%).
(4) Preparation of Compound C20
Compound 2-3 (15 g,26.7 mmol), 4-pyridineboronic acid (3.3 g,26.7 mmol), potassium carbonate (7.4 g,54.3 mmol), tris dibenzylideneacetone dipalladium (0.22 g,0.3 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.24 g,0.6 mmol) were added to a 1L flask containing 200mL of 1, 4-dioxane and 20mL of water, the nitrogen was replaced and the reaction was heated under reflux for 4 hours under a nitrogen atmosphere, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound C20 (12.1 g, yield 72%). Calculated molecular weight: 633.20, found C/Z:633.2.
Synthesis example 3:
Synthesis of Compound C42
(1) Preparation of Compound 3-1
The compound 2-bromo-4-chlorobenzaldehyde (218 g,1.0 mol) was added to a 5L flask containing 2L glacial acetic acid, and ammonium acetate (154 g,2.0 mol) and diphenyldione (210 g,1.0 mol) were slowly added in portions with stirring at room temperature, and the reaction was stirred at 120℃for 4 hours under reflux after the addition, and TLC monitoring showed completion of the reaction. After the reaction solution was cooled to room temperature, it was slowly poured into 4L of water to precipitate a large amount of solid, and the solid was purified by column chromatography after suction filtration to give compound 3-1 (381 g, yield 93%).
(2) Preparation of Compound 3-2
Compound 3-1 (40.8 g,100 mmol), o-bromophenol (17.2 g,100 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after replacing nitrogen, cuprous iodide (0.38 g,2.0 mmol) and phenanthroline (0.79 g,4.0 mmol) were added, respectively, replacing nitrogen 4 times, stirring and refluxing at 110℃for 12 hours, and TLC monitored the end point of the reaction. After the reaction is cooled to room temperature, the mixture is slowly poured into 2L of cold water to precipitate a large amount of solid, the solid after suction filtration is respectively leached with water and ethanol for three times, the solid is dried, and the compound 3-2 (24 g, yield 57%) is obtained after column chromatography separation and purification after drying.
(3) Preparation of Compound 3-3
4-Bromo-4 ' -cyanobiphenyl (25.7 g,100 mmol), pinacol biborate (38.1 g,150 mmol), potassium acetate (19.6 g,200 mmol) were charged into a 1L flask containing 400mL of 1, 4-dioxane, and palladium acetate (0.45 g,2.0 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (1.6 g,4.0 mmol) were added after nitrogen substitution with stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was stirred at reflux for 12 hours, and TLC monitored the end of the reaction. The 1, 4-dioxane was removed by rotary evaporation, water and methylene chloride were added to the mixture, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 3-3 (22.2 g, yield 73%).
(4) Preparation of Compound C42
Compound 3-2 (15 g,35.7 mmol), compound 3-3 (10.9 g,35.7 mmol), potassium carbonate (9.9 g,71.4 mmol), dibenzylideneacetone dipalladium (0.26 g,0.36 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.3 g,0.72 mmol) were added to a 1L flask containing 200mL of 1, 4-dioxane and 20mL of water, the nitrogen was replaced and the reaction was heated under reflux for 4 hours under nitrogen atmosphere, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound C42 (15.4 g, yield 77%). Calculated molecular weight: 563.20, found C/Z:563.2.
Synthesis example 4:
Synthesis of Compound C64
(1) Preparation of Compound 4-1
2-Amino-4, 6-diphenylpyrazine (24.7 g,100 mmol) was dissolved in 250mL dioxane, and then added dropwise thereto with the temperature kept at not higher than 15℃in a 500mL three-necked flask, ethoxycarbonyl isothiocyanate (15.8 g,120 mmol) was stirred at room temperature overnight. TLC detection was complete, dioxane was concentrated, ethanol was stirred and washed, and after filtration, column chromatography was used to isolate and purify compound 4-1 (29.1 g, yield 77%).
(2) Preparation of Compound 4-2
Hydroxylamine hydrochloride (19.2 g,288 mmol) was added to a 500mL three-necked flask, followed by 150mL ethanol and 150mL methanol, and then triethylamine (19.2 g,288 mmol) was added in portions and stirred at room temperature for one hour. Compound 4-1 (24 g,64 mmol) was added and heated to reflux for about 4h, after which the reaction was completed by TLC and cooled to room temperature. Filtering, eluting with water, eluting with ethanol, drying, and separating and purifying by column chromatography to obtain compound 4-2 (15.2 g, 93%).
(3) Preparation of Compound 4-3
CuBr 2 (23.4 g,106 mmol) and 200mL of acetonitrile (MeCN) were added to a 500mL single-necked flask, followed by slow dropwise addition of tert-butyl nitrite (11 g,106 mmol) and stirring at 50℃for one hour, followed by addition of compound 4-2 (15.2 g,53 mmol) in portions and stirring at 50℃was continued. After 3h reaction, TLC detection, complete reaction of compound 4-2, cooling the reaction solution, pouring into 1L of water, precipitating a large amount of yellowish green solid, filtering, eluting with ethanol, drying, extracting the separated liquid with DCM, drying the organic phase with anhydrous sodium sulfate, and purifying by column chromatography to obtain compound 4-3 (15 g, yield 81%).
(4) Preparation of Compounds 4-4
The compound 2-bromo-4-chlorobenzaldehyde (21.8 g,100 mol) was added to a 500mL flask containing 200mL of glacial acetic acid, and ammonium acetate (15.4 g,200 mmol) and phenanthrenequinone (20.8 g,100 mmol) were slowly added in portions with stirring at room temperature, and the reaction was stirred at 120℃under reflux for 4 hours after the addition, and TLC monitoring showed complete reaction. After the reaction solution was cooled to room temperature, it was slowly poured into 4L of water to precipitate a large amount of solid, and the solid was purified by column chromatography after suction filtration to give Compound 4-4 (33.2 g, yield 82%).
(5) Preparation of Compounds 4-5
Compound 4-4 (33 g,76 mmol), o-bromophenyl thiophenol (14.3 g,76 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after nitrogen substitution, cuprous iodide (0.29 g,1.5 mmol) and phenanthroline (0.6 g,3.0 mol) were added, respectively, nitrogen substitution was performed 4 times, and the reaction was refluxed with stirring at 110℃for 12 hours, and TLC monitored the end of the reaction. After the reaction is cooled to room temperature, slowly pouring the mixture into 2L of cold water to precipitate a large amount of solid, leaching the solid after suction filtration with water and ethanol for three times respectively, drying the solid, and separating and purifying by column chromatography after drying to obtain the compound 4-5 (24.4 g, yield 74%).
(6) Preparation of Compounds 4-6
Compound 4-5 (24 g,55.3 mmol), pinacol biborate (21 g,83 mmol), potassium acetate (10.8 g,110.6 mmol) were added to a 1L flask containing 300mL of 1, 4-dioxane, and palladium acetate (0.25 g,1.1 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.9 g,2.2 mmol) was added after displacing nitrogen with stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was stirred at reflux for 12 hours, and TLC monitored the end of the reaction. The 1, 4-dioxane was removed by rotary evaporation, water and methylene chloride were added to the mixture, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 4-6 (21 g, yield 76%).
(7) Preparation of Compound C64
Compound 4-3 (10 g,28.6 mmol), compound 4-6 (15 g,28.6 mmol), potassium carbonate (7.9 g,57.2 mmol), and tetraphenylpalladium phosphate (0.34 g,0.29 mmol) were added to a flask containing 100mL of toluene, 20mL of ethanol and 20mL of water, nitrogen was replaced, and the reaction was heated under reflux under a nitrogen atmosphere for 4 hours, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound C64 (16.3 g, yield 85%). Calculated molecular weight: 670.19, found C/Z:670.2.
Synthesis example 5:
Synthesis of Compound C67
(1) Preparation of Compound 5-1
50G (256 mmol,1.0 eq) of 2, 4-dichloroquinazoline was added to a 1L single-necked flask, 400mL of methylene chloride was added, the temperature was reduced to 0℃in an ice bath, 64g (630 mmol,3.0 eq) of triethylamine was added, the reaction mixture was stirred until it became clear, 18.6g (316 mmol,1.5 eq) of hydrazine hydrate was added dropwise to the ice bath during the reaction, a solid was gradually precipitated, stirring was carried out for 3 hours, TLC monitored the reaction, the raw material disappeared, 4.0L of water was added, and stirring was continued for 1 hour. Filtration and drying gave compound 5-1 (33 g, yield: 81%).
(2) Preparation of Compound 5-2
33G of Compound 5-1 (170 mmol,1.0 eq), benzaldehyde 19.8g (187 mmol,1.1 eq) and 500mL of ethanol were added to a 1.0L single-necked flask, and stirring was continued for 30 minutes after the solution was clarified, and TLC monitored for disappearance of starting material. 60g (187 mmol,1.1 eq) of iodobenzene diacetic acid (lower than 20 ℃ C. When fed) are added in portions. After the addition, stirring overnight, gradually precipitating solid, after TLC monitoring reaction, filtering, eluting the filter cake with ethanol until the filtrate is colorless clear liquid, eluting with Petroleum Ether (PE) for 2-3 times, and drying to obtain the compound 5-2 (39 g, yield: 82%).
(3) Preparation of Compound 5-3
The compound 2-bromo-4-chlorobenzaldehyde (21.8 g,100 mmol) was added to a 500mL flask containing 200mL glacial acetic acid, ammonium acetate (15.4 g,200 mmol) and diethyl oxalate (14.6 g,100 mmol) were slowly added in portions with stirring at room temperature, and the reaction was stirred at 120℃under reflux for 4 hours after the addition, and TLC monitoring showed the reaction was complete. After the reaction solution was cooled to room temperature, it was slowly poured into 4L of water to precipitate a large amount of solid, and the solid was purified by column chromatography after suction filtration to give compound 5-3 (22.5 g, yield 88%).
(4) Preparation of Compounds 5-4
Compound 5-3 (22 g,86 mmol), 4-chloro-2-bromophenylthiophenol (18.9 g,86 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after nitrogen substitution, cuprous iodide (0.33 g,1.7 mmol) and phenanthroline (0.67 g,3.4 mol) were added, respectively, nitrogen substitution was performed 4 times, and reflux reaction was stirred at 110℃for 12 hours, and TLC monitored for the end of the reaction. After the reaction is cooled to room temperature, slowly pouring the mixture into 2L of cold water to precipitate a large amount of solids, leaching the filtered solids with water and ethanol for three times respectively, drying the solids, and separating and purifying the dried solids by column chromatography to obtain the compound 5-4 (21 g, yield 77%).
(5) Preparation of Compounds 5-5
Compound 5-4 (20.6 g,80 mmol), pinacol biborate (50.8 g,200 mmol), potassium acetate (15.7 g,160 mmol) were added to a 1L flask containing 500mL of 1, 4-dioxane, and palladium acetate (0.36 g,1.6 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (1.3 g,3.2 mmol) was added after displacing nitrogen with stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was stirred at reflux for 12 hours, and TLC monitored the end of the reaction. The 1, 4-dioxane was removed by rotary evaporation, water and methylene chloride were added to the mixture, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 5-5 (30.5 g, yield 76%).
(6) Preparation of Compound C67
Compound 5-2 (10 g,35.7 mmol), compound 5-5 (8.5 g,17 mmol), potassium carbonate (9.9 g,71.4 mmol), dibenzylideneacetone dipalladium (0.22 g,0.3 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.24 g,0.6 mmol) were added to a 1L flask containing 200mL of 1, 4-dioxane and 20mL of water, the nitrogen was replaced and the reaction was heated under reflux for 4 hours under nitrogen atmosphere, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound C67 (9.8 g, yield 78%). Calculated molecular weight: 738.21, found C/Z:738.2.
Comparative Synthesis example 1
Synthesis of Compound D1:
(1) Preparation of Compound D1-1
The compound diacetone (21 g,100 mmol) was added to a 500mL flask containing 200mL glacial acetic acid, ammonium acetate (15.5 g,200 mmol) was added slowly in portions with stirring at room temperature, and the reaction was stirred at 120℃for 4 hours under reflux, and TLC monitoring showed complete reaction. After the reaction solution was cooled to room temperature, it was slowly poured into 1L of water to precipitate a large amount of solid, and the solid was purified by column chromatography to give Compound D1-1 (37.5 g, yield 92%).
(2) Preparation of Compounds D1-2
Compound D1-1 (35 g,85.8 mmol), o-bromophenol (14.7 g,85.8 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after replacing nitrogen, cuprous iodide (0.33 g,1.7 mmol) and phenanthroline (0.68 g,3.4 mol) were added, respectively, replacing nitrogen 4 times, stirring and refluxing at 110℃for 8 hours, and TLC monitored the reaction end point. After the reaction is cooled to room temperature, the mixture is slowly poured into 2L of cold water to precipitate a large amount of solid, the solid after suction filtration is respectively leached with water and ethanol for three times, the solid is dried, and the dried solid is separated and purified by column chromatography to obtain the compound D1-2 (25.4 g, yield 68%).
(3) Preparation of Compound D1
Compound D1-2 (15 g,34.4 mmol), phenylboronic acid (5.0 g,41.2 mmol), potassium carbonate (9.5 g,68.8 mmol), dibenzylideneacetone dipalladium (0.62 g,0.68 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.53 g,1.3 mmol) were added to a 1L flask containing 200mL of 1, 4-dioxane and 20mL of water, the nitrogen was replaced and the reaction was heated under reflux for 4 hours under nitrogen atmosphere, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound D1 (12.3 g, yield 75%). Calculated molecular weight: 478.15, found C/Z:478.2.
Comparative Synthesis example 2
Synthesis of compound D2:
(1) Preparation of Compound D2-1
The compound 4-chloro-2-bromoaniline (20.5 g,100 mmol), o-bromophenol (17.1 g,100 mmol) and 300mL of N, N-dimethylformamide were added to a 1L flask, after nitrogen substitution, cuprous iodide (0.39 g,2.0 mmol) and phenanthroline (0.80 g,4.0 mol) were added, respectively, nitrogen substitution was performed 4 times, and reflux reaction was stirred at 110℃for 6 hours, and TLC monitored for the end of the reaction. After the reaction is cooled to room temperature, the mixture is slowly poured into 2L of cold water to precipitate a large amount of solid, the solid after suction filtration is respectively leached with water and ethanol for three times, the solid is dried, and the compound D2-1 (18.3 g, yield 79%) is obtained after column chromatography separation and purification after drying.
(2) Preparation of Compound D2-2
Compound D2-1 (18 g,78 mmol), pinacol biborate (29.7 g,117 mmol), potassium acetate (21.5 g,156 mmol) was added to a 1L flask containing 300mL of 1, 4-dioxane, and palladium acetate (0.36 g,1.6 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (1.3 g,3.2 mmol) was added after displacing nitrogen with stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was stirred at reflux for 8 hours, and TLC monitored the end of the reaction. The 1, 4-dioxane was removed by rotary evaporation, water and methylene chloride were added to the mixture, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound D2-2 (19.4 g, yield 77%).
(3) Preparation of Compound D2
Compound D2-2 (15 g,46.3 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (12.3 g,46.3 mmol), potassium carbonate (12.7 g,92.6 mmol), and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (365 mg,0.5 mmol) were added to a flask containing 200mL of tetrahydrofuran and 50mL of water, the nitrogen was replaced and the reaction was heated under reflux for 4 hours under nitrogen atmosphere, and TLC showed the reaction to be complete. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound D2 (16.3 g, yield 82%). Calculated molecular weight: 429.12, found C/Z:429.1.
Comparative Synthesis example 3
Synthesis of compound D3:
The compound 4-spirobifluorene boronic acid (15 g,41.6 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (11.1 g,41.6 mmol), potassium carbonate (11.4 g,83 mmol) and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (292 mg,0.4 mmol) were added to a flask containing 200mL tetrahydrofuran and 50mL water, the nitrogen was replaced and the reaction was heated to reflux under nitrogen for 6 hours, and TLC showed complete reaction. The precipitated solid was filtered, rinsed with water and ethanol, and dried, and then purified by column chromatography to give compound D3 (17.8 g, yield 78%). Calculated molecular weight: 549.22, found C/Z:549.2.
Example 1
The embodiment provides a preparation method of an organic electroluminescent device, which specifically comprises the following steps:
the glass plate coated with the ITO transparent conductive layer was sonicated in commercial cleaners, rinsed in deionized water, and rinsed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding surface with low-energy cation beam;
Placing the glass substrate with the anode in a vacuum cavity, vacuumizing until the pressure is less than 10 -5 Pa, and vacuum evaporating HI-3 serving as a hole injection layer on the anode layer film by using a multi-source co-evaporation method, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm;
Vacuum evaporation HT-4 is carried out on the hole injection layer to serve as a first hole transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 40nm;
vacuum evaporating HT-14 on the first hole transport layer to obtain a second hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 10nm;
Vacuum evaporating a luminescent layer of the device on the second hole transport layer, wherein the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material BFH-4 is regulated to be 0.1nm/s by utilizing a multi-source co-evaporation method, the evaporation rate of the dye BFD-6 is set to be 5% in proportion, and the total film thickness of evaporation is 20nm;
vacuum evaporating ET-17 on the luminescent layer as a hole blocking layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 5nm;
evaporating the compound C1 and ET-57 serving as an electron transport layer on the hole blocking layer by utilizing a multi-source co-evaporation method, adjusting the evaporation rate of the compound C1 to be 0.1nm/s, setting the ratio of the evaporation rate of the compound C1 to the evaporation rate of the ET-57 to be 100% (the ratio of the evaporation rates of the C1 and the ET-57 is 1:1), and enabling the total film thickness of the evaporation to be 23nm;
LiF with the thickness of 1nm is vacuum evaporated on an Electron Transport Layer (ETL) to serve as an electron injection layer, and an Al layer with the thickness of 80nm serves as a cathode of the device.
Examples 2-15, comparative examples 1-3 differ from example 1 only in the replacement of compound C1 with other compounds, see in particular table 1.
Performance test:
The driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples were measured using a Photo Research company PR 750 type optical radiometer, an ST-86LA type luminance meter (photoelectric instrumentation Co., ltd., beijing) and a Keithley4200 test system at the same luminance. Specifically, the voltage was raised at a rate of 0.1V per second, and the driving voltage, which is the voltage when the luminance of the organic electroluminescent device reached 1000cd/m 2, was measured, while the current density at that time was measured; the ratio of brightness to current density is the current efficiency;
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the case that other materials are the same in the structure of the organic electroluminescent device, the organic electroluminescent device provided by the embodiment of the invention has higher current efficiency and lower driving voltage, wherein the current efficiency is 6.42-7.22cd/A, and the driving voltage is 3.81-4.38V.
The parent nucleus of the compound is an electron-deficient large conjugated structure of imidazo nitrogen sulfur (oxygen) hetero-seven-membered cyclodiphenyl, ar is connected with the parent nucleus by a single bond or L, so that the whole compound has higher electron injection and migration performance, the device has higher current efficiency and lower driving voltage, and the technical effect of the invention can not be realized by replacing the parent nucleus or Ar with other structures (comparative examples 1-3).
As is clear from comparison of examples 1 and 2 and 5, the electron-deficient large conjugated structure of the parent imidazo-nitrogen-sulfur (oxy) hetero-hepta-cycloacene is connected with the triazine electron-deficient group (Ar), the voltage of the device is lower, the current efficiency is higher, and examples 2 and 5 change the substituent group (Ar) into phenanthrene and cyano-substituted phenyl groups so that the voltage is increased and the current efficiency is reduced, because in the electron-deficient large conjugated structure of the specific imidazo-nitrogen-sulfur (oxy) hetero-hepta-cycloacene, the triazine group with lower electron density is more obvious for improving the electron injection and mobility.
As is clear from comparison of example 1 and example 3, when the substituents R 1 and R 2 are not present on the parent imidazole (example 3), the current efficiency is reduced by 0.12cd/a, but the voltage is greatly reduced by 0.2V, which is due to the better electron-deficient and plane conjugation of the whole molecule, and the lower molecular weight makes the resistance of electron transport smaller and the lower voltage on the premise of ensuring the electron injection and migration properties.
Comparative example 1 and example 6 show that the voltage is substantially the same when X is O (example 6) as compared to the electron transport material with X being S (example 1), but the current efficiency of example 1 is higher than that of example 6 due to the higher conjugated electron cloud density of the aza-seven-membered ring than the aza-oxygen seven-membered ring.
As is clear from comparison of example 5 and example 7, after the substituents R 1 and R 2 on the imidazole of the parent nucleus are changed from phenyl to 4-cyanophenyl (example 7), the driving voltage of the device is reduced, and the current efficiency is higher, because the 4-cyanophenyl of the linear three-dimensional structure is connected with the single bond of the parent nucleus to form a symmetrical linear structure as a whole, the electron injection and migration efficiency is further improved, and thus the driving voltage is reduced and the current efficiency is also improved by 10%.
The experimental data show that the novel organic material provided by the invention is used as an electron transport material of an organic electroluminescent device, is an organic luminescent functional material with good performance, and has a wide application prospect.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (26)

1. A compound characterized by having a structure represented by formula (1);
in the formula (1), X is S or O;
in the formula (1), ar is selected from any one of substituted or unsubstituted C8-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl and cyano;
in the formula (1), L is selected from any one of single bond, substituted or unsubstituted C6-C60 arylene and substituted or unsubstituted C3-C60 heteroarylene;
In formula (1), each of R 1 and R 2 is independently selected from any one of hydrogen, deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 chain alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
In the formula (1), R is selected from any one of deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 chain alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
in the formula (1), n is an integer of 0to 7, and m is an integer of 0 or 1;
in the formula (1), Y represents a single bond;
Ar, L, R 1、R2 and R, wherein each substituted group is independently selected from one or a combination of at least two of halogen, cyano, nitro, hydroxy, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 fused ring heteroaryl.
2. The compound according to claim 1, wherein the compound has any one of structures represented by formulas (a) to (h);
each R 3-R9 is independently selected from any one of hydrogen, deuterium, halogen, cyano, C2-C20 alkenyl, C2-C20 alkynyl, nitro, C1-C20 alkyl, C3-C21 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
In R 3-R9, the substituted groups are each independently selected from one or a combination of at least two of halogen, cyano, nitro, hydroxy, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 fused ring heteroaryl;
the Ar, L and R 1、R2 have the same limit as claim 1.
3. The compound according to claim 1 or 2, wherein Ar is selected from any one of substituted or unsubstituted C8-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, cyano.
4. A compound according to claim 1 or 2, wherein Ar is selected from substituted or unsubstituted C3-C30 electron-deficient heteroaryl or cyano.
5. A compound according to claim 1 or 2, wherein Ar is selected from cyano or any of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
6. A compound according to claim 1 or 2, wherein Ar is selected from cyano or any of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
7. The compound of claim 6, wherein Ar is selected from substituted or unsubstituted triazinyl.
8. The compound according to claim 1 or 2, wherein L is selected from the group consisting of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group.
9. A compound according to claim 1 or 2, wherein L is selected from a single bond or a substituted or unsubstituted C6-C30 arylene group.
10. The compound according to claim 1 or 2, wherein L is selected from any one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group.
11. A compound according to claim 1 or 2, wherein L is substituted or unsubstituted phenylene and Ar is cyano.
12. The compound of claim 1 or 2, wherein R 1 and R 2 are each independently selected from any one of hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
13. The compound of claim 12, wherein in R 1 and R 2, the substituted or unsubstituted C6-C30 aryl is cyano-substituted C6-C30 aryl.
14. The compound of claim 12, wherein in R 1 and R 2, the substituted or unsubstituted C6-C30 aryl is cyano-substituted phenyl.
15. The compound according to claim 1 or 2, wherein R 1 and R 2 are each independently selected from hydrogen or any one of the following substituted or unsubstituted groups:
16. The compound according to claim 1 or 2, wherein R 1 and R 2 are each independently selected from hydrogen, cyano-substituted phenyl or any of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
17. The compound of claim 1, wherein R is selected from a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted C3-C30 heteroaryl.
18. The compound of claim 1, wherein R is selected from any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
19. The compound of claim 2, wherein each R 3-R9 is independently selected from any one of hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
20. The compound of claim 2, wherein each R 3-R9 is independently selected from hydrogen or any one of the following substituted or unsubstituted groups:
wherein the wavy line marks represent the bond of the group.
21. The compound of claim 1, wherein the compound has any one of the structures shown as C1 to C75:
22. Use of a compound according to any one of claims 1-21, wherein the compound is for an organic electronic device;
The organic electronic device comprises an organic electroluminescent device, an optical sensor, a solar cell, an illumination element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet scanner or electronic paper.
23. The use according to claim 22, wherein the compound is used in an organic electroluminescent device.
24. The use according to claim 23, wherein the compound is used as an electron transport material in the organic electroluminescent device.
25. An organic electroluminescent device, characterized in that it comprises a substrate, a first electrode, a second electrode and at least one organic layer between the first electrode and the second electrode, the organic layer comprising at least one compound according to any one of claims 1-21.
26. The organic electroluminescent device of claim 25, wherein the organic layer comprises an electron transport layer comprising at least one compound of any one of claims 1-21.
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