CN113968848A - Organic compound for organic electroluminescent device and application thereof - Google Patents

Organic compound for organic electroluminescent device and application thereof Download PDF

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CN113968848A
CN113968848A CN202010714947.4A CN202010714947A CN113968848A CN 113968848 A CN113968848 A CN 113968848A CN 202010714947 A CN202010714947 A CN 202010714947A CN 113968848 A CN113968848 A CN 113968848A
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孙恩涛
方仁杰
刘叔尧
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Beijing Eternal Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
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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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
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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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K85/649—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

An organic compound having a structure represented by (1):
Figure DDA0002597810370000011
l is a single bond, a substituted or unsubstituted arylene group of C6-C30, or a substituted or unsubstituted heteroarylene group of C3-C30; ar is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C3-C60; x is O or S; r1‑R3Each independently is H, deuterium, halogen, cyano, chain alkyl of C1-C20, alkene of C2-C20A cycloalkyl group of C3-C21, an alkynyl group of C2-C20, an alkoxy group of C1-C20, a substituted or unsubstituted aryl group of C6-C60, or a substituted or unsubstituted heteroaryl group of C3-C60; r2Optionally fused to the aromatic ring in which X is present; m, n, o are each independently an integer from 1 to the maximum allowed, but the hydrogens in the x positions in the formula cannot be substituted.

Description

Organic compound for organic electroluminescent device and application thereof
Technical Field
The present invention relates to an organic compound, and more particularly, to an organic compound for an organic electroluminescent device and an application thereof.
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.
In order to prepare an OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device need to be innovated, and photoelectric functional materials in the OLED device need to be continuously researched and innovated, so that functional materials with higher performance can be 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.
Disclosure of Invention
Problems to be solved by the invention
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.
The invention aims to provide an organic compound which has better hole blocking capability and can effectively improve the injection and transmission of electrons from an electron transport layer to a light-emitting layer.
It is another object of the present invention to provide an organic electroluminescent material having high luminous efficiency and low activation voltage using the above organic compound of the present invention as a hole blocking material.
Means for solving the problems
As a result of intensive studies to solve the above-mentioned problems in the prior art, the inventors of the present invention have found that when a new material comprising 11- (2-furan/thiophene or derivatives thereof) substituted benzocarbazole as an electron donating group and a linking group such as phenylene and an electron deficient group such as triazine, pyrimidine, quinazoline and the like is used as a hole blocking material, the lifetime and luminous efficiency of the obtained organic electroluminescent device are significantly improved, and have completed the present invention.
Specifically, one of the objects of the present invention is to provide an organic compound having a structure represented by (1):
Figure BDA0002597810360000021
wherein the content of the first and second substances,
l is a single bond, a substituted or unsubstituted arylene group of C6-C30, or a substituted or unsubstituted heteroarylene group of C3-C30;
ar is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C3-C60;
x is O or S;
R1-R3each independently is H, deuterium, halogen, cyano, chain alkyl of C1-C20, alkenyl of C2-C20, cycloalkyl of C3-C21, alkynyl of C2-C20, alkoxy of C1-C20, substituted or unsubstituted aryl of C6-C60 or substituted or unsubstituted heteroaryl of C3-C60; r2Optionally fused to the aromatic ring in which X is present;
m, n, o are each independently an integer from 1 up to the maximum allowed, but the hydrogens in the positions of the formula are not substituted;
when the substituted or unsubstituted group has a substituent, the substituent is selected from one or a combination of two or more of halogen, cyano, nitro, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 thioalkoxy, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C30 aryl, C6-C30 arylamino, C3-C30 heteroaryl, and C3-C30 heteroarylamino.
The organic electroluminescent device prepared by the organic compound has longer service life and higher efficiency, and can meet the requirements of current panel manufacturing enterprises on high-performance materials. The specific reason why the above organic compound is excellent in performance when used as a hole blocking layer material in an organic electroluminescent device is not clear, and is presumed as follows.
According to the compound, ortho furan or thiophene or derivatives thereof are introduced into the 11-position of the benzocarbazole which is an electron-donating group, so that an oxygen atom or a sulfur atom in a molecule can form a hydrogen bond with an adjacent hydrogen atom (1-position, namely an x-position) in the molecule, the plane conjugation of the electron-donating group is increased, and the accumulation among molecules is facilitated, so that the capability of injecting and transmitting electrons from an electron transmission layer to a light-emitting layer is improved. And secondly, the hole blocking material with the D-A structure has higher triplet state energy level, and can effectively prevent excitons from diffusing from the light emitting layer to the electron transport layer, so that the device obtains lower starting voltage and higher current efficiency.
The organic compound of the present invention preferably has a structure shown in (2):
Figure BDA0002597810360000031
the meanings and ranges of the respective groups and letters in formula (2) are the same as those in formula (1).
Formula (2) can also be represented by the following two sub-formulae:
Figure BDA0002597810360000032
in the compound of the present invention, the 2-position of the substituted or unsubstituted furyl or thienyl group is preferably linked to the 11-position of the benzocarbazole, which is more favorable for the formation of a hydrogen bond than the 3-position, and is more favorable for improving the ability of injecting and transporting electrons from the electron transport layer to the light-emitting layer.
The organic compound of the present invention preferably L is a substituted or unsubstituted arylene group of C6-C30, or a substituted or unsubstituted heteroarylene group of C3-C30; more preferably L is phenylene or biphenylene; further preferred is a meta-phenylene group or a meta-biphenylene group.
By setting L to phenylene in the meta-position or biphenylene in the meta-position, the obtained compound is excellent in the performance of an organic electroluminescent device obtained when used as a hole-blocking layer material. The principle is not clear, and presumably, the meta-connection mode not only ensures that the molecules have a certain pi-pi conjugation effect, but also avoids the increase of the rigidity of the molecules caused by large conjugated pi bonds, thereby ensuring the good film-forming property of the molecules in vapor deposition. In other words, meta-linkages provide the molecules with the proper pi-conjugation effect to maximize the transport properties of the material.
The organic compound of the present invention is preferably Ar selected from one of the following substituted or unsubstituted groups:
Figure BDA0002597810360000041
the dotted lines in each of the above groups indicate the attachment site of Ar to L, the dotted lines from the center of the ring outward indicate that the attachment site can be at any permissible position on the ring, and the dotted lines across several rings indicate that the attachment site can be at any permissible position on the rings.
Ar is further preferably selected from one of the following substituted or unsubstituted groups:
Figure BDA0002597810360000042
when the substituted or unsubstituted group has a substituent, the substituent is a phenyl group, a naphthyl group, or a biphenyl group.
In the compound of the present invention, by defining Ar as the above group, diffusion of excitons from the light-emitting layer to the electron-transporting layer can be more effectively prevented, thereby enabling the device to obtain a lower activation voltage.
The organic compound of the present invention is preferably R1And R3Is hydrogen, R2Is hydrogen, methyl, phenyl or is fused with the aromatic ring in which X is positioned to form benzofuranyl or benzothienyl.
The organic compound of the present invention is preferably m-1, n-1, or o-1.
In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent or with a plurality of substituents, and when a plurality of substituents are present, they may be selected from different substituents or may be all or partially the same. When the same expression mode is involved in the invention, the same meanings are provided, and the selection ranges of the substituents are shown above and are not repeated.
It is to be noted that, in the present specification, the expression of Ca-Cb represents that the group has the number of carbon atoms of a to b, and generally the number of carbon atoms does not include the number of carbon atoms of the substituent unless otherwise specified. In the present invention, unless otherwise specified, the expressions of chemical elements generally include the concept of chemically identical isotopes, such as the expression "hydrogen", and also include the concept of chemically identical "deuterium" and "tritium".
In the present specification, the expression of the loop structure marked by a dotted line indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can be bonded.
In the present specification, unless otherwise specified, both aryl and heteroaryl groups include monocyclic and fused rings.
In the present specification, the substituted or unsubstituted aryl group of C6-C60 is preferably a substituted or unsubstituted aryl group of C6-C30, more preferably a C6-C20, and may be a monocyclic aryl group in the group consisting of phenyl, biphenyl, tetrabiphenyl, and terphenyl. In particular, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl. The substituted or unsubstituted aryl group having C6 to C60 may be a condensed ring aryl group selected from the group consisting of naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, celtyl, peryl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, terphenyl, fluorenyl, spirobifluorenyl, phenanthrenyl, pyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, and spiroisoindenyl. Specifically, the naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracene group is selected from the group consisting of 1-tetracene, 2-tetracene, and 9-tetracene.
In the present specification, arylene is to be construed as referring to the corresponding aryl group except that one more hydrogen has been removed than the corresponding aryl group.
In the present specification, a heteroatom generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably N, O, S.
In the present specification, the substituted or unsubstituted heteroaryl group having C3 to C60 is preferably a substituted or unsubstituted heteroaryl group having C3 to C30, more preferably a heteroaryl group having C4 to C20, and may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like, and specific examples thereof include: monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, pyridyl, pyrazolyl, imidazolyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl and the like; benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenazinyl, indazolyl, benzimidazolyl, naphthoimidazolyl, phenanthrimidazolyl, pyridoimidazolyl, pyrazinimidazolyl, quinoxalimidazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, benzopyrazinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazoanthrenyl, 2, 7-diazepanyl, 2, 3-diazapyranyl, 1, 6-diazapyranyl, 1, 8-diazepanyl, 4,5,9, 10-tetraazaperyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, benzotriazolyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole and other fused ring heteroaryl groups, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole or indolocarbazole.
In the present specification, heteroarylene is to be taken in the context of the corresponding heteroaryl group, with the exception that one more hydrogen has been removed than the corresponding heteroaryl group.
In the present specification, the C1-C20 alkyl group is preferably a C1-C12 alkyl group, more preferably a C1-C6 alkyl group, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl and the like.
In the present specification, the cycloalkyl group of C3-C12 includes monocycloalkyl and polycycloalkyl groups, preferably C4-C8 cycloalkyl groups, and may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the C1-C20 alkoxy group is preferably a C1-C10 alkoxy group, more preferably a C1-C6 alkoxy group, and examples thereof include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like, among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy, more preferably methoxy.
In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, etc., preferably fluorine.
The compounds of the above formula of the present invention preferably have a structure represented by C1-C69:
Figure BDA0002597810360000061
Figure BDA0002597810360000071
Figure BDA0002597810360000081
Figure BDA0002597810360000091
the second object of the present invention is to provide the use of the compound according to the first object for the application in organic electronic devices.
Preferably, the organic electronic device includes 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 an organic electroluminescent device.
Preferably, the compound is used as a hole blocking material in the organic electroluminescent device.
The compound of the invention has a deeper HOMO energy level and a higher triplet state energy level, can effectively block holes and excitons, can effectively improve the injection of electrons from an electron transport layer to a light-emitting layer, and is suitable for being used as a hole blocking material, but is not limited to the hole blocking material.
It is a further object of the present invention to provide an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic functional layers interposed between the first electrode and the second electrode, wherein the organic functional layer contains the compound of the general formula of the present invention represented by any one of the above general formulae or contains the compound represented by each of the above specific formulae.
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 organic functional layers, and a cathode layer sequentially formed on the substrate; the organic functional layer comprises a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking 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 hole blocking layer; wherein the hole-blocking layer contains the compound represented by the general formula (1) of the present invention.
Effects of the invention
The compound provided by the invention takes 11- (2-furan/thiophene or derivatives thereof) substituted benzocarbazole as an electron donating group, and forms a novel hole blocking material with electron deficient groups such as triazine, pyrimidine, quinazoline and the like through a connecting group, particularly meta-phenyl or meta-biphenyl. Ortho furan or thiophene or derivatives thereof are introduced into the 11-position of the benzocarbazole in the electron-donating group, so that oxygen atoms or sulfur atoms in molecules can form hydrogen bonds with adjacent hydrogen atoms in the molecules, the planar conjugation of the electron-donating group is increased, and the accumulation among molecules is facilitated, thereby improving the capability of injecting and transmitting electrons from the electron transport layer to the light-emitting layer. In addition, the hole blocking material with the D-A structure has a high triplet state energy level, and can effectively prevent excitons from diffusing from the light emitting layer to the electron transport layer, so that the excellent effects of high light emitting 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 technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The synthetic route of the compound shown by the general formula of the invention is as follows:
Figure BDA0002597810360000111
in the first step, 1-naphthalene boric acid and 2, 3-dichloronitrobenzene are subjected to Suzuki coupling reaction to generate an intermediate M-1; in the second step, the intermediate M-1 undergoes a reduction ring-closing reaction under the action of triphenylphosphine to synthesize an intermediate M-2; in the third step, M-2 and the diboron acid pinacol ester react to synthesize an intermediate M-3; the fourth step, the intermediate M-3 and bromofuran and derivatives thereof (thiophene and derivatives thereof) are synthesized into an intermediate M-4 through a Suzuki reaction; the fifth step is that intermediate M-4 and electron-deficient heteroaryl halide are synthesized into final products through Buchwald reaction.
The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).
Synthesis example 1:
synthesis of Compound C1
Figure BDA0002597810360000112
(1) Preparation of Compound 1-1
The compound 1-naphthalene boronic acid (344g, 2mol), 2, 3-dichloronitrobenzene (566g, 2mol) and potassium carbonate (828g, 3mol) were added to a flask containing 1, 4-dioxane/water (8L/1L), nitrogen was replaced with tetratriphenylphosphine palladium (11.5 g, 10mmol) while stirring at room temperature, nitrogen was replaced three times after the addition was completed, the reaction was refluxed for 5 hours with stirring, and the end point of the reaction was monitored by TLC. Removing 1, 4-dioxane by rotary evaporation under reduced pressure, dissolving with dichloromethane, and separating. The organic phase was dried over anhydrous sodium sulfate, filtered, the solvent was removed under reduced pressure, 5L of methanol was added thereto, the mixture was stirred at room temperature overnight, a brown solid was precipitated by filtration, and the mixture was air-dried to obtain Compound 1-1(526g, yield 93%).
(2) Preparation of Compounds 1-2
Compound 1-1(283g, 1mol) and triphenylphosphine (655g, 2.5mol) were added to a flask containing 5L of o-dichlorobenzene, and the reaction was heated under reflux for 10 hours with stirring, and the end of the reaction was monitored by TLC. The solvent was removed by rotary evaporation under reduced pressure, and the resulting product was purified by column chromatography to give 1-2(136g, yield 54%) as a pale yellow solid.
(3) Preparation of Compounds 1-3
Compound 1-2(126g, 0.5mol), pinacol diboron ester (191g, 0.75mmol) and potassium acetate (147g, 1.5mol) were charged into a flask containing 3L of 1, 4-dioxane, and after replacing nitrogen with stirring at room temperature, palladium acetate (2.2g, 10mmol) and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (8.2g, 20mmol) were added. After the addition, nitrogen was replaced three times, the reaction was refluxed with stirring for 8 hours, and the end point of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, and the mixture was separated with water and dichloromethane, and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 1-3(142g, yield 83%).
(4) Preparation of Compounds 1-4
Compound 1-3(34.3g, 0.1mol), 2-bromofuran (14.6g, 0.1mol), and potassium carbonate (41.4g, 0.3mol) were charged into a flask containing toluene/ethanol/water 300mL/60mL/60mL, and after replacing nitrogen with stirring at room temperature, tetratriphenylphosphine palladium (1.1g, 1mmol) was added, after completion of addition, nitrogen was replaced three times, and the reaction was refluxed for 7 hours with stirring, and the end point of the reaction was monitored by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure and purified by column chromatography to give tan compounds 1-4(18g, yield 63%).
(5) Preparation of Compound C1
Compound 1-4(5.7g, 20mmol), 2(3(3' -bromobiphenyl)) -4, 6-diphenyl-1, 3, 5-triazine (9.3g, 20mmol), sodium tert-butoxide (5.8g, 60mmol) were added to a flask containing 150ml of toluene, after replacement of nitrogen, Pd2(dba)3(183mg, 0.2mmol), tri-tert-butylphosphine (0.4mmol, toluene solution) were added, replacement of nitrogen was completed, and the reaction was refluxed for 10 hours under nitrogen atmosphere, and TLC showed completion of the reaction. After cooling to room temperature, water was added to quench the reaction. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compound C1(10.8g, 81% yield). Calculated molecular weight: 666.2, respectively; measured value m/z: 667.1(M + 1).
Synthesis example 2:
synthesis of Compound C22
Figure BDA0002597810360000131
(1) Preparation of Compound 2-1
Compound 1-3(20g, 58.3mmol), 2-bromobenzofuran (11.4g, 58.3mmol) and potassium carbonate (24.1g, 175mmol) were charged into a flask containing toluene/ethanol/water 250mL/50mL/50mL, and after replacement of nitrogen with stirring at room temperature, palladium tetratriphenylphosphine (0.7g, 0.6mmol) was added, after completion of addition, nitrogen was replaced three times, and the reaction was refluxed for 5 hours with TLC monitoring of the end point of the reaction. Cooling to room temperature and separating. The organic phases were extracted with ethyl acetate, the combined organic phases were dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure and column chromatography was performed to purify the resulting product to obtain brown compound 2-1(11.8g, yield 61%).
(2) Preparation of Compound 2-2
The compound 1-chloro-2-phenyl-4- (4-biphenyl) -1,3, 5-triazine (34.3g, 0).1mol), 3-Chlorobenzeneboronic acid (15.6g, 0.1mol) and potassium carbonate (41.4g, 0.3mol) were added to a flask containing tetrahydrofuran/water 300mL/50mL, and after replacing nitrogen with stirring at room temperature, Pd (dppf) Cl was added2(732mg, 1mmol), after the addition was completed, nitrogen was replaced three times, the reaction was refluxed with stirring for 4 hours, and the end of the reaction was monitored by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the resulting product was purified by column chromatography to give white compound 2-2(36g, yield 86%).
(3) Preparation of Compound C22
Compound 2-1(6.7g, 20mmol), compound 2-2(8.4g, 20mmol), sodium tert-butoxide (5.8g, 60mmol) were added to a flask containing 150ml of toluene, after replacement of nitrogen, Pd2(dba)3(183mg, 0.2mmol), tri-tert-butylphosphine (0.4mmol, toluene solution) were added three times, and the reaction was refluxed under nitrogen for 15 hours, and TLC showed completion of the reaction. After cooling to room temperature, water was added to quench the reaction. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compound C22(11g, 77% yield). Calculated molecular weight: 716.3, respectively; measured value m/z: 717.3(M + 1).
Synthesis example 3:
synthesis of Compound C37
Figure BDA0002597810360000141
(1) Preparation of Compound 3-1
Compound 1-3(15.4g, 45mmol), 2-bromothiophene (7.3g, 45mmol), and potassium carbonate (18.6g, 135mmol) were charged into a flask containing toluene/ethanol/water 250mL/50mL/50mL, and after replacement of nitrogen gas at room temperature with stirring, palladium tetratriphenylphosphine (520mg, 0.45mmol) was added, after completion of addition, nitrogen gas was replaced three times, and the reaction was refluxed for 7 hours with stirring, and the end point of the reaction was monitored by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the compound 3-1(8.7g, yield 65%) was purified by column chromatography.
(2) Preparation of Compound 3-2
The compound 1-chloro-4-phenylquinazoline (24g, 0.1mol), 3-chloro-3-biphenylboronic acid (23.2g, 0.1mol) and potassium carbonate (41.4g, 0.3mol) were charged into a flask containing tetrahydrofuran/water 250mL/50mL, and after replacing nitrogen with stirring at room temperature, Pd (dppf) Cl was added2(732mg, 1mmol), after the addition was completed, nitrogen was replaced three times, the reaction was refluxed with stirring for 2 hours, and the end of the reaction was monitored by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the compound 3-2 was purified by column chromatography (32.5g, yield 83%).
(3) Preparation of Compound C37
Compound 3-1(6g, 20mmol), compound 3-2(7.8g, 20mmol), sodium tert-butoxide (5.8g, 60mmol) were added to a flask containing 150ml of toluene, after replacement of nitrogen, Pd2(dba)3(366mg, 0.4mmol), tri-tert-butylphosphine (0.8mmol, toluene solution) were added three times, and the reaction was refluxed under nitrogen for 12 hours, as indicated by TLC completion of the reaction. After cooling to room temperature, water was added to quench the reaction. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compound C37(9.8g, 75% yield). Calculated molecular weight: 655.2; measured value m/z: 656.2(M + 1).
Synthesis example 4:
synthesis of Compound C50
Figure BDA0002597810360000151
(1) Preparation of Compound 4-1
Compound 1-3(15.4g, 45mmol), 2-bromo-3-methylthiophene (7.9g, 45mmol), and potassium carbonate (18.6g, 135mmol) were charged into a flask containing toluene/ethanol/water 250mL/50mL/50mL, and after replacement of nitrogen gas with stirring at room temperature, palladium tetratriphenylphosphine (520mg, 0.45mmol) was added, after completion of addition, nitrogen gas was replaced three times, and the reaction was refluxed for 14 hours with monitoring of the end of the reaction by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the compound 4-1(8.5g, yield 60%) was purified by column chromatography.
(2) Preparation of Compound 4-2
The compounds o-bromonitrobenzene (100.5g, 0.5mol), m-bromoaniline (102.6g, 0.6mol), sodium acetate (147g, 1.5mol) were added to the flask, and the reaction was stirred for 8 hours while heating to 180 ℃ with replacement of nitrogen, and TLC showed completion of the reaction. Cooling to room temperature, diluting with ethyl acetate, vacuum filtering, vacuum drying the filtrate, washing the crude product with methanol, and drying to obtain compound 4-2(92g, yield 63%).
(3) Preparation of Compound 4-3
Compound 4-2(58.4g, 0.2mol) was dissolved in a flask containing 500mL of tetrahydrofuran, and 500mL of an aqueous solution containing sodium dithionite (174g, 1mol) was added dropwise with stirring under nitrogen at room temperature, and the reaction was continued for 6 hours with stirring after completion of the addition, and TLC showed completion of the nitro reduction reaction. To the reaction system was added 300mL of an aqueous solution of sodium hydrogencarbonate (33.6g, 0.4mol), 200mL of an ethyl acetate solution of benzoyl chloride (33.6g, 0.24mol) was added dropwise, and the reaction was stirred for 3 hours after completion of the addition. TLC showed the reaction was complete. Separating, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, filtering, removing the solvent by rotary evaporation under reduced pressure, and performing column chromatography on the crude product to obtain the compound 4-3(49g, yield 67%).
(4) Preparation of Compound 4-4
Compound 4-3(36.6g, 0.1mol) was dissolved in a flask containing 500mL of xylene, p-toluenesulfonic acid (8.6g, 0.05mol) was added, water was separated from the water separator, the reaction was refluxed for 6 hours with stirring, and TLC showed completion of the reaction. The solvent was removed under reduced pressure, washed with ethanol, and dried to give compound 4-4(29.5g, yield 85%).
(5) Preparation of Compounds 4-5
Compound 4-4(17.4g, 50mmol), 3-chlorobenzeneboronic acid (7.8g, 50mmol), potassium carbonate (20.7g, 150mmol) were added to a flask containing toluene/ethanol/water 300mL/50mL/50mL, after displacing nitrogen, Pd (PPh3)4(578mg, 0.5 mmol) was added, again displacing nitrogen three times and the reaction was heated under nitrogen at reflux for 8 hours, TLC indicated completion of the reaction. Cooling to room temperature, separating, extracting the organic phase with ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and purifying by column chromatography to obtain compound 4-5(16g, yield 84%).
(6) Preparation of Compound C50
Compound 4-1(6.3g, 20mmol), compound 4-5(7.6g, 20mmol), sodium tert-butoxide (5.8g, 60mmol) were added to a flask containing 150ml of toluene, after replacement of nitrogen, Pd2(dba)3(183mg, 0.2mmol), tri-tert-butylphosphine (0.4mmol, toluene solution) were added three times, and the reaction was refluxed under nitrogen for 10 hours, and TLC showed completion of the reaction. After cooling to room temperature, water was added to quench the reaction. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compound C50(9.3g, 71% yield). Calculated molecular weight: 657.2, respectively; measured value m/z: 658.1(M + 1).
Synthesis example 5:
synthesis of Compound C64
Figure BDA0002597810360000161
(1) Preparation of Compound 5-1
Compound 1-3(17.2g, 50mmol), 2-bromo-4-methylthiophene (8.8g, 50mmol), and potassium carbonate (20.7g, 150mmol) were charged into a flask containing toluene/ethanol/water 300mL/60mL/60mL, nitrogen was replaced with stirring at room temperature, palladium tetratriphenylphosphine (1.1g, 1mmol) was added, nitrogen was replaced three times after completion of the addition, the reaction was refluxed for 10 hours, and the end of the reaction was monitored by TLC. Cooling to room temperature and separating. The organic phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the compound was purified by column chromatography to give 5-1(8.3g, yield 53%).
(2) Preparation of Compound C64
Compound 5-1(6.3g, 20mmol), 2(3(3' -bromobiphenyl)) -4, 6-diphenyl-1, 3, 5-triazine (9.3g, 20mmol), sodium tert-butoxide (5.8g, 60mmol) were added to a flask containing 150ml of toluene, after replacement of nitrogen, Pd2(dba)3(366mg, 0.4mmol), tri-tert-butylphosphine (0.8mmol, toluene solution) were added, replacement of nitrogen was completed, and the reaction was refluxed for 18 hours under nitrogen atmosphere, and TLC showed completion of the reaction. After cooling to room temperature, water was added to quench the reaction. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give compound C64(10.4g, 75% yield). Calculated molecular weight: 696.2, respectively; measured value m/z: 697.2(M + 1).
Comparative example 2:
synthesis of Compound D2
Figure BDA0002597810360000171
Comparative example Synthesis of Compound D2A synthesis similar to that of example 1 was used except that 2, 4-dichloronitrobenzene was used instead of 2, 3-dichloronitrobenzene as the starting material in the first step.
Device embodiments
Next, the organic electroluminescent device will be explained in detail:
the OLED device 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 multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL); wherein the HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.
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), and aromatic amine derivatives as shown below in HT-1 to HT-51; or any combination thereof.
Figure BDA0002597810360000181
Figure BDA0002597810360000191
Figure BDA0002597810360000201
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-51 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-51 may also be used to dope one or more of the compounds HI-1-HI-3 described below.
Figure BDA0002597810360000211
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.
Figure BDA0002597810360000212
Figure BDA0002597810360000221
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, the combination of one or more of BFD-1 through BFD-24 listed below.
Figure BDA0002597810360000222
Figure BDA0002597810360000231
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 PH-1 to PH-85.
Figure BDA0002597810360000232
Figure BDA0002597810360000241
Figure BDA0002597810360000251
Figure BDA0002597810360000261
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.
Figure BDA0002597810360000271
Figure BDA0002597810360000281
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.
Figure BDA0002597810360000282
Figure BDA0002597810360000291
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-YPD-11 listed below.
Figure BDA0002597810360000292
In one aspect of the invention, an Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but is not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described above; mixtures of one or more compounds from HT-1 to HT-51 and one or more compounds from PH-47 to PH-77 may also be used, but are not limited thereto.
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-65 listed below.
Figure BDA0002597810360000301
Figure BDA0002597810360000311
Figure BDA0002597810360000321
Figure BDA0002597810360000331
In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds from ET-1 to ET-65 or one or more compounds from PH-1 to PH-46; mixtures of one or more compounds from ET-1 to ET-65 with one or more compounds from PH-1 to PH-46 may also be used, but are not limited thereto.
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、Mg。
the preparation process of the organic electroluminescent device in the embodiment is as follows:
device example 1:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing until the pressure is less than 10-5Pa, vacuum evaporating and plating HI-3 with the thickness of 10nm on the anode layer film to be used as a hole injection layer;
vacuum evaporating and plating 40nm HT-4 on the hole injection layer to be used as a first hole transport layer of the device;
vacuum evaporating and plating 10nm HT-14 on the first hole transport layer to be used as a second hole transport layer of the device;
a 20nm luminous layer is vacuum evaporated on the second hole transport layer and comprises a main body material BFH-4 and a dye material BFD-6, the evaporation rate of the main body material BFH-4 is 0.1nm/s, and the evaporation rate of the dye BFD-6 is 5% of that of the main body material;
vacuum evaporating 5nm of the compound C1 of the invention on the luminescent layer to be used as a hole blocking layer of the device;
evaporating 23nm compounds ET-61 and ET-57 (the ratio of evaporation rates of ET-61 and ET-57 is 1:1) on the hole blocking layer by using a multi-source co-evaporation method to form an electron transport layer;
LiF with the thickness of 1nm is evaporated on the Electron Transport Layer (ETL) in vacuum to be used as an electron injection layer, and an aluminum layer with the thickness of 80nm is used as a cathode of the device. The evaporation rate of all the organic layers and LiF is 0.1nm/s, and the evaporation rate of the metal aluminum is 1 nm/s.
Device examples 2 to 5 were fabricated in the same manner as in example 1, except that the compound C1 of the present invention used in the hole-blocking layer was replaced with C22, C37, C50, and C64.
Devices comparative examples 1 and 2 were fabricated in the same manner as in device example 1, except that the compound C1 of the present invention used in the hole-blocking layer was replaced with the prior art compounds D1 and D2.
Figure BDA0002597810360000341
Compound D1 is commercially available, and synthesis of compound D2 is described above.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the test system measured the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples at the same brightness. 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 1000 cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency.
The properties of the organic electroluminescent devices prepared in examples 1 to 5 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
Hole blocking material Required luminance (cd/m)2) Voltage (V) Current efficiency (Cd/A)
Example 1 C1 1000.00 4.31 7.56
Example 2 C22 1000.00 4.41 7.40
Example 3 C37 1000.00 4.47 7.12
Example 4 C50 1000.00 4.36 7.50
Example 5 C64 1000.00 4.38 7.47
Example 6 C68 1000.00 4.52 7.09
Comparative example 1 D1 1000.00 4.98 6.11
Comparative example 2 D2 1000.00 4.56 6.95
As can be seen from table 1, under the condition that the material schemes and the preparation processes of other functional layers in the structure of the organic electroluminescent device are completely the same, the voltage of the organic electroluminescent device using the compound of the present invention as the hole blocking material is reduced, and the efficiency is significantly improved, compared with the organic electroluminescent device using the compound of comparative example 1 as the hole blocking material. The specific reason is not clear, and it is presumed that in the electron-donating group of the present invention, by introducing ortho-furan or thiophene or its derivatives into the 11-position of benzocarbazole in the electron-donating group, oxygen atoms or sulfur atoms in molecules can form hydrogen bonds with adjacent hydrogen atoms in the molecules, thereby increasing the planar conjugation of the electron-donating group, facilitating the inter-molecular accumulation, and improving the ability of injecting and transmitting electrons from the electron transport layer to the light-emitting layer. And secondly, the hole blocking material with the D-A structure has higher triplet state energy level, and can effectively prevent excitons from diffusing from the light emitting layer to the electron transport layer, so that the device obtains lower starting voltage and higher current efficiency. In addition, the D-A group is bridged through meta-phenyl or meta-biphenyl, so that certain flexibility of molecules is kept while certain pi conjugation effect of the molecules is ensured, evaporation film-forming performance of materials is facilitated, and good carrier mobility of the molecules is ensured.
The organic electroluminescent devices of comparative examples 1 and 2 used compounds D1 and D2, respectively, as hole-blocking materials. Unlike the parent nucleus of the compound of the present invention, the compound D1 does not incorporate ortho furan, thiophene or derivatives thereof, and thus the resulting device has a higher voltage and a lower current efficiency than the present invention. In fact, compound D1 is not suitable for use as a hole blocking material. Compound D2 differs from the compound of the present invention in that the ortho furan is attached to the 10-position of the mother nucleus instead of the 11-position, resulting in higher voltage and lower current efficiency of the organic electroluminescent device of comparative example 2. The reason for this is not clear, but is presumed as follows. The compound of the invention introduces ortho furan or thiophene or derivatives thereof into the 11 th position of benzocarbazole in the electron-donating group, so that oxygen atoms or sulfur atoms in molecules can form hydrogen bonds with adjacent hydrogen atoms in the molecules, the plane conjugation of the electron-donating group is increased, and the accumulation among molecules is facilitated, thereby improving the capability of injecting and transmitting electrons from the electron transport layer to the light-emitting layer. Whereas the ortho furan in compound D2 was attached to the 10-position of the parent nucleus, hydrogen bonds in the compound of the present invention could not be formed, and thus the organic electroluminescent device of comparative example 2 was inferior in performance to the present invention.
The experimental data show that the novel organic material is used as a hole blocking material of an organic electroluminescent device, is an organic luminescent functional material with good performance, and has wide application prospect.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.

Claims (10)

1. An organic compound having a structure represented by (1):
Figure FDA0002597810350000011
wherein the content of the first and second substances,
l is a single bond, a substituted or unsubstituted arylene group of C6-C30, or a substituted or unsubstituted heteroarylene group of C3-C30;
ar is substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C3-C60;
x is O or S;
R1-R3each independently is H, deuterium, halogen, cyano, chain alkyl of C1-C20, alkenyl of C2-C20, cycloalkyl of C3-C21, alkynyl of C2-C20, alkoxy of C1-C20, substituted or unsubstituted aryl of C6-C60 or substituted or unsubstituted heteroaryl of C3-C60; r2Optionally fused to the aromatic ring in which X is present;
m, n, o are each independently an integer from 1 up to the maximum allowed, but the hydrogens in the positions of the formula are not substituted;
when the substituted or unsubstituted group has a substituent, the substituent is selected from one or a combination of two or more of halogen, cyano, nitro, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 thioalkoxy, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C30 aryl, C6-C30 arylamino, C3-C30 heteroaryl, and C3-C30 heteroarylamino.
2. The organic compound according to claim 1, having a structure shown in (2):
Figure FDA0002597810350000012
the meanings and ranges of the respective groups and letters in formula (2) are the same as those in formula (1).
3. The organic compound of claim 1 or 2, wherein L is a substituted or unsubstituted arylene group of C6-C30, or a substituted or unsubstituted heteroarylene group of C3-C30;
l is preferably phenylene or biphenylene, more preferably meta-phenylene or meta-biphenylene.
4. An organic compound according to claim 1 or 2, wherein Ar is selected from one of the following substituted or unsubstituted groups:
Figure FDA0002597810350000021
5. the organic compound of claim 4, wherein Ar is selected from one of the following substituted or unsubstituted groups:
Figure FDA0002597810350000022
when the substituted or unsubstituted group has a substituent, the substituent is a phenyl group, a naphthyl group, or a biphenyl group.
6. An organic compound according to claim 1 or 2, wherein R is1And R3Is hydrogen, R2Is hydrogen, methyl, phenyl or is fused with the aromatic ring in which X is positioned to form benzofuranyl or benzothienyl.
7. An organic compound according to claim 1 or 2, wherein m-1, n-1, and o-1.
8. The organic compound of claim 1, having a structure represented by C1-C69:
Figure FDA0002597810350000031
Figure FDA0002597810350000041
Figure FDA0002597810350000051
Figure FDA0002597810350000061
9. use of the organic compound according to any one of claims 1 to 8 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;
the organic compounds are preferably used as hole blocking materials in organic electroluminescent devices.
10. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic functional layers interposed between the first electrode and the second electrode, characterized in that the organic functional layer contains the organic compound according to any one of claims 1 to 8.
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