CN112778281A - Compound and application thereof - Google Patents
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- CN112778281A CN112778281A CN201911087783.0A CN201911087783A CN112778281A CN 112778281 A CN112778281 A CN 112778281A CN 201911087783 A CN201911087783 A CN 201911087783A CN 112778281 A CN112778281 A CN 112778281A
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Abstract
The invention relates to a compound and application thereof, wherein the compound has a structure shown in a formula I, a carbazole structure of multiple conjugated condensed rings is used as a mother nucleus of the compound, and an electron-withdrawing group quinoxaline group or a quinazoline group is substituted on N of carbazole, the structure can improve the planarity of molecules, reduce the transmission barrier of current carriers, and is matched with a specific electron-withdrawing group, so that a device containing the compound has the advantages of low voltage and high efficiency, and in addition, the molecules have a rigid structure of multiple conjugated condensed rings, the molecular chemical stability is strong, the thermal stability is excellent, and the performance in the device also shows better service life.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound and application thereof.
Background
In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them well suited for fabrication on flexible substrates, allowing for the design and production of aesthetically pleasing and crunchy optoelectronic products, with unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have been developed particularly rapidly, and have been commercially successful in the field of information display. The OLED can provide three colors of red, green and blue with high saturation, and a full-color display device manufactured by using the OLED does not need an additional backlight source and has the advantages of gorgeous color, light weight, softness and the like.
The core of the OLED device is a thin film structure containing various organic functional materials. 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. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light.
People have developed various organic materials, and the organic materials are combined with various peculiar device structures, so that the carrier mobility can be improved, the carrier balance can be regulated and controlled, the electroluminescent efficiency can be broken through, and the attenuation of the device can be delayed. For quantum mechanical reasons, common fluorescent emitters mainly utilize singlet excitons generated when electrons and holes are combined to emit light, and are still widely applied to various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet excitons and singlet excitons, which are called phosphorescent emitters, and the energy conversion efficiency can be increased by up to four times as compared with conventional fluorescent emitters. The thermal excitation delayed fluorescence (TADF) technology can still effectively utilize triplet excitons to achieve higher luminous efficiency without using a metal complex by promoting the conversion of triplet excitons to singlet excitons. Thermal excitation sensitized fluorescence (TASF) technology also achieves higher luminous efficiency by sensitizing the emitter by energy transfer using TADF-like materials.
However, the existing red host materials have problems: the carrier transport barrier is high, a high voltage is required, and the luminous efficiency and the stability of the molecular structure are also poor.
Therefore, there is a need to develop new material systems to meet the increasing requirements for the photoelectric performance and the service life of the OLED device.
Disclosure of Invention
An object of the present invention is to provide a compound which, when applied to an organic electroluminescent device, has excellent photoelectric properties and a long service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a compound, which has a structure shown in a formula I;
in the formula I, the Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH and CR1、CR2Or one of N;
the R is1One selected from substituted or unsubstituted C6 to C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) aryl, substituted or unsubstituted C3 to C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroaryl, substituted or unsubstituted C6 to C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylamino, substituted or unsubstituted C3 to C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroarylamino;
the R is2Selected from C1-C12 (e.g. C2, C3, C4, C5, C6, C7, C8, C9, C10) chain alkyl, C3-C12 (e.g. C4, C5, C6, C7, C8, C9, C10) cycloalkylC1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino;
in the formula I, Ar has a structure shown in a formula II or a formula III;
in the formula II, L1One selected from a single bond, a substituted or unsubstituted C6 to C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylene group, a substituted or unsubstituted C3 to C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroarylene group;
in the formula II, m is an integer of 0-5, such as 1, 2, 3,4 and the like;
when m is an integer of 2 or more, i.e. the mother nucleus is substituted with two or more R3When two or more R are present3May be the same group or different groups, n and R4The same process is carried out;
in the formula III, L2One selected from substituted or unsubstituted C6 to C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylene, substituted or unsubstituted C3 to C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroarylene;
in the formula III, n is an integer of 0-5, such as 1, 2, 3,4, etc.;
in the formulae II and III, the R3And R4Each independently selected from substituted or unsubstituted C-C (e.g., C, etc.) aryl, substituted or unsubstituted C-C (e.g., C, etc.) heteroaryl, substituted or unsubstituted C-C (e.g., C, etc.) chain alkyl, substituted or unsubstituted C-C (e.g., C, etc.) cycloalkyl, substituted or unsubstituted C-C (e.g., C, etc.) alkoxyOne of halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) arylamino, substituted or unsubstituted C3-C30 heteroarylamino;
in formula II and formula III, represents the access bond of the group;
when a substituent is present in the above groups, the substituent is selected from the group consisting of halogen, cyano, chain alkyl of C to C (e.g., C, etc.), alkoxy of C to C (e.g., C, etc.), thioalkoxy of C to C (e.g., C, etc.), arylamino of C to C (e.g., C, etc.), heteroarylamino of C to C (e.g., C, etc.), monocyclic aryl of C to C, condensed ring aryl of C to C (e.g., C, heteroaryl, C, etc.), monocyclic aryl of C to C (e.g., C, etc.) C12, C14, C16, C18, C20, C26, C28, etc.) fused ring heteroaryl or a combination of at least two thereof. The "substituted or unsubstituted" group may be substituted with one substituent or a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected.
In the present invention, the heteroatom of heteroaryl is generally referred to as N, O, S.
In the present invention, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linkage can be formed.
The invention provides a novel compound, which takes a carbazole structure of multiple conjugated condensed rings as a mother nucleus, can improve the planarity of molecules and reduce the transmission barrier of current carriers, so that a device has the advantages of low voltage and high efficiency;
in addition, an electron-withdrawing group quinoxaline group (formula II) or a quinazoline group (III) is substituted on N of carbazole, and the fixed matching combination reduces the energy level overlapping region of HOMO and LUMO of the material, brings smaller energy difference between a singlet state and a triplet state, reduces the non-radiative transition of the host material, further reduces the voltage and improves the efficiency.
When Ar is selected from the structures of formula III, a bridging group L must be provided between the carbazole and the quinazoline2The arrangement of the bridging group between the two groups can distort the molecular space configuration, and the distorted molecular configuration can avoid the luminescence quenching effect caused by the pi-pi interaction between molecules in an aggregation state, thereby realizing the high-efficiency luminescence of the organic compound.
Preferably, said Y is1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH and CR1Or one of N; wherein R is1With the same selection ranges as before.
Preferably, said Y is1、Y2、Y3And Y4Each independently selected from CH and CR1Or one of N, Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH or CR1(ii) a Wherein R is1With the same selection ranges as before.
Preferably, said Y is1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH.
Preferred Y in the invention1～Y16Are both CH, since the HOMO energy level of such molecules is positive when both are CHThe material energy level of the material is well matched with that of the adjacent layer, the material has good transmission performance, and the HOMO energy level can be changed after a substituent is added on the donor core.
Preferably, said R is1One selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thienyl, and substituted or unsubstituted triarylamine, preferably one selected from substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thienyl, and substituted or unsubstituted triarylamine.
Preferably, Ar has a structure represented by formula IV or formula V;
in formula IV and formula V, represents an access bond of the group;
the R is3、R4、L1And L2Each independently having the same ranges as formula II and formula III.
Preferably, Ar has a structure represented by formula IV.
Preferably, Ar has a structure represented by formula V.
Preferably, said R is3And R4Each independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted phenanthryl.
Preferably, said R is3And R4Each independently selected from one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, pyridyl and phenanthryl.
Preferably, said L1Selected from the group consisting of single bond, phenylene, pyridylene, pyridine-substituted phenylene, cyano-substituted phenyleneOne of (1) and (b), preferably a single bond or a phenylene group.
Preferably, said L2One selected from phenylene, naphthylene, pyridine substituted phenylene and cyano substituted phenylene, preferably phenylene.
Preferably, the compound has the following structure represented by P1 to P80:
the second purpose of the invention is to provide the application of the compound in the first purpose, and the compound is applied to an organic electroluminescent device.
Preferably, the compound is used as a material of a light emitting layer of the organic electroluminescent device, preferably as a host material of the light emitting layer.
The invention also provides an organic electroluminescent device which comprises a substrate, a first electrode, a second electrode and at least one organic layer positioned between the first electrode and the second electrode, wherein the organic layer contains at least one compound for one purpose.
Preferably, the organic layer includes a light-emitting layer containing at least one compound described for one of the purposes.
Preferably, the compound serves as a host material of the light-emitting layer.
Specifically, an organic electroluminescent device (OLED) includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1 to HI-3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI-1 to HI-3 described below.
The light emitting layer includes a light emitting dye (i.e., Dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more of GPH-1 to GPH-80.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
The OLED organic material layer may further include 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).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li2O、Cs2CO3BaO, Na, Li and/or Ca.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel compound, which takes a carbazole structure of multiple conjugated condensed rings as a mother nucleus, can improve the planarity of molecules and reduce the transmission barrier of current carriers, so that a device has the advantages of low voltage and high efficiency;
in addition, an electron-withdrawing group quinoxaline group (formula II) or a quinazoline group (III) is substituted on N of carbazole, and the fixed matching combination reduces the energy level overlapping region of HOMO and LUMO of the material, brings smaller energy difference between a singlet state and a triplet state, reduces the non-radiative transition of the host material, further reduces the voltage and improves the efficiency.
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.
A representative synthetic route for the compounds of formula I of the present invention is as follows:
wherein, Ar and Y1To Y16All have the same meaning as in formula I.
More specifically, the following synthetic examples provide methods for the preparation of specific compounds:
synthesis example 1: synthesis of Compound P1
Adding 10-bromobenzo [ g ] chrysene (100mmol), o-nitrobenzoic acid (120mmol), potassium carbonate (45mmol), dioxane (200mL), tetrakis (triphenylphosphine) palladium (1.2 g) and water (50mL) into a reaction bottle, heating until refluxing reaction is carried out for 6h, monitoring the reaction completion by Thin Layer Chromatography (TLC), adding into water, extracting with ethyl acetate, and concentrating an organic phase to obtain an intermediate A.
And adding 200mL of the intermediate A (60mmol), triphenylphosphine (180mmol) and o-dichlorobenzene into a reaction bottle, heating until reflux reaction is carried out for 4h, monitoring by TLC (thin layer chromatography) for complete reaction, directly concentrating to dryness, and carrying out column chromatography purification to obtain B.
Adding the intermediate B (30mmol), 2- (4-fluorophenyl) -4-phenylquinazoline (35mmol), cesium carbonate (60mmol) and N, N-dimethylformamide (DMF, 150mL) into a reaction bottle, carrying out reflux reaction for 8h, cooling to room temperature after complete reaction, pouring the reaction liquid into water, filtering, washing a filter cake with ethanol once, and recrystallizing with toluene to obtain the compound P1.
Synthesis example 2: synthesis of Compound P15
The synthesis method was different from that of synthesis example 1 in that 2- (4-fluorophenyl) -4-phenylquinazoline was replaced with an equivalent amount of 2- (2-fluoropyridin-5-yl) -4-phenylquinazoline to obtain compound P15.
Synthesis example 3: synthesis of Compound P22
The difference between the synthesis method and the synthesis example 1 is that 2- (4-fluorophenyl) -4-phenylquinazoline is replaced by equal amount of 2- (3-biphenyl) -3-chloroquinoxaline to obtain a compound P22.
Synthesis example 4: synthesis of Compound P27
The synthesis method was different from that of synthesis example 1 in that 2- (4-fluorophenyl) -4-phenylquinazoline was replaced with an equivalent amount of 2- (4-fluorophenyl) -3-phenylquinazoline to obtain compound P27.
Synthesis example 5: synthesis of Compound P41
Adding 200mL of the intermediate B (30mmol), 3-bromo-5-cyanobenzene (30mmol), potassium carbonate (50mmol) and N, N-Dimethylformamide (DMF) into a reaction bottle for reflux reaction for 3h, pouring the reaction liquid into water for filtration, washing a filter cake with methanol, and drying to obtain an intermediate 41-A.
Adding 41-A (20mmol), pinacol diboride (30mmol), potassium acetate (30mmol), ([1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, 0.2mmol) and 300mL of dioxane into a reaction bottle, refluxing and reacting for 4 hours under the protection of nitrogen, adding water after the reaction is finished, extracting with dichloromethane, separating an organic phase, and concentrating to obtain an intermediate 41-B.
Adding 41-B (15mmol), 2-chloro-3-phenylquinoxaline (20mmol), potassium carbonate (30mmol), dioxane (150mL), tetrakis (triphenylphosphine) palladium (0.5 g) and water (30mL) into a reaction bottle, heating to reflux for 6h, monitoring by TLC to complete the reaction, directly filtering after cooling, dissolving a filter cake by dichloromethane, then carrying out column chromatography filtration, and after concentration, recrystallizing xylene to obtain P41.
Synthesis example 6: synthesis of Compound P53
The difference between the synthesis method and the synthesis example 1 is that o-nitrobenzeneboronic acid is replaced by 4-nitro-3-pyridine pinacol ester with equal substance amount to obtain a compound P53.
Synthesis example 7:
synthesis of Compound P72
And adding the intermediate B (30mmol) and 200mL of DMF into a reaction bottle, cooling to 0 ℃, dropwise adding N-bromosuccinimide (NBS, 35mmol), reacting at room temperature for 2 hours after dropwise adding, and pouring into water after HPLC monitoring reaction is finished to obtain an intermediate 72-A by filtration.
Adding 72-A (20mmol), triphenylamine-4-boric acid (20mmol), potassium carbonate (30mmol), dioxane (150mL), tetrakis (triphenylphosphine) palladium (0.5 g) and water (30mL) into a reaction bottle, heating to reflux for 4h, monitoring by TLC to complete the reaction, cooling, adding water and dichloromethane for extraction, and concentrating an organic phase to obtain 72-B.
Adding 72-B (15mmol), 2-chloro-3-phenylquinoxaline (20mmol), cesium carbonate (30mmol) and DMF (150mL) into a reaction bottle, refluxing for reaction for 8h, cooling to room temperature after the reaction is completed, pouring the reaction liquid into water for filtration, washing filter cake with ethanol once, and recrystallizing with toluene to obtain the compound P72.
In order to verify the certainty of the molecular structure, we confirmed the molecular structure by elemental analysis (measuring instrument: Sammerfed FLASH 2000CHNS/O organic element analyzer) and mass spectrometry information (measuring instrument: ZAB-HS type mass spectrometer measurement, manufactured by Micromass Co., UK), as shown in Table 1.
TABLE 1
| Compound (I) | Elemental analysis (%) | Mass spectrometry |
| P1 | C，89.00；H，4.51；N，6.49 | 647.2 |
| P15 | C，87.01；H，4.35；N，8.64 | 648.2 |
| P22 | C，89.00；H，4.51；N，6.49 | 647.2 |
| P27 | C，89.00；H，4.51；N，6.49 | 647.2 |
| P41 | C，87.48；H，4.19；N，8.33 | 672.2 |
| P53 | C，87.01；H，4.35；N，8.64 | 648.2 |
| P72 | C，88.43；H，4.70；N，6.87 | 814.3 |
Example 1
The embodiment provides an organic electroluminescent device, and the specific preparation method is as follows:
ultrasonically treating the glass plate coated with the ITO transparent conducting layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent, baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10-5Pa, performing vacuum thermal evaporation on the anode layer film in sequence to obtain a 10nm HT-4: HI-3(97/3, w/w) mixture as a hole injection layer, a 60nm compound HT-4 as a hole transport layer, a 40nm compound P1: RPD-8(100:3, w/w) binary mixture as a light emitting layer, a 25nm compound ET-46: ET-57(50/50, w/w) mixture as an electron transport layer, 1nm LiF as an electron injection layer, and 150nm metal aluminum as a cathode. The total evaporation rate of all the organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.
Examples 2 to 10 and comparative examples 1 to 2 differ from example 1 only in the replacement of the host material of the light emitting layer, as detailed in table 2.
Wherein, the structures of the host materials of the light emitting layers in comparative examples 1 and 2 are as follows:
compounds C1, C2 are detailed in WO2017109722a1, CN109956876A, respectively;
performance testing
(1) The driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples were measured at the same luminance using a PR 750 type photoradiometer of Photo Research corporation, a ST-86LA type luminance meter (photoelectric instrument factory of university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and the current density as measured when the organic electroluminescent device reached 10mA/cm2Voltage at once drivingDynamic voltage, and measuring the brightness at the moment; the ratio of the brightness to the current density is the current efficiency;
the results of the above performance tests are shown in table 2.
TABLE 2
As shown in Table 2, when the compound provided by the invention is used as a main material of a light-emitting layer of an organic electroluminescent device, the device has lower driving voltage and higher current efficiency, wherein the driving voltage is 3.5-3.8V, and the current efficiency is 14.3-15.8 cd/A.
Compared with the compound C1 (comparative example 1), the compound P1 (example 1) is structurally similar, but differs from the compound C1 in the ring closing direction of carbazole, and has two different material structures, and the specific mother nucleus structure of the invention enables the compound P1 to have better performance in voltage and efficiency. Presumably, the steric hindrance of the material is increased due to the parent-nucleus structure of the invention, so that the mutual quenching of excitons is prevented, and the performance of the material is improved.
Compared with all the examples, the light-emitting layer host material C2 in the comparative example 2 introduces two electron-withdrawing groups of carbazole group and triazine group, and the device performance of the comparative example 2 is poorer, specifically, the voltage is increased, and the current efficiency is reduced, so that the invention proves that the specific electron-withdrawing group is substituted on the N of carbazole, and the device performance can be effectively improved. The fixed collocation combination reduces the energy level overlapping region of HOMO and LUMO of the material of the invention, brings smaller energy difference of singlet state and triplet state, reduces the non-radiative transition of the host material, reduces the voltage of the host material and has higher efficiency.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. A compound having a structure according to formula I;
in the formula I, the Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH and CR1、CR2Or one of N;
the R is1One selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino and substituted or unsubstituted C3-C30 heteroarylamino;
the R is2One selected from C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl and amino;
in the formula I, Ar has a structure shown in a formula II or a formula III;
in the formula II, L1One selected from single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
in the formula II, m is an integer of 0-5;
in the formula III, L2One selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
in the formula III, n is an integer of 0-5;
in the formulae II and III, the R3And R4Each independently selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino and substituted or unsubstituted C3-C30 heteroarylamino;
in formula II and formula III, represents the access bond of the group;
when the above groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C6-C30 condensed ring heteroaryl.
2. The compound of claim 1, wherein Y is1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH and CR1Or one of N; wherein R is1Having the same limits as in claim 1.
3. The compound of claim 1, wherein Y is1、Y2、Y3And Y4Each independently selected from CH and CR1Or one of N, the Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH or CR1(ii) a Wherein R is1Having the same limits as in claim 1.
4. The compound of claim 1, wherein Y is1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15And Y16Each independently selected from CH.
5. A compound according to claims 1-3, wherein R is1One selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thienyl, and substituted or unsubstituted triarylamine, preferably one selected from substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thienyl, and substituted or unsubstituted triarylamine.
6. The compound of claim 1, wherein Ar has a structure of formula IV or formula V;
in formula IV and formula V, represents an access bond of the group;
the R is3、R4、L1And L2Each independently having the same limitations as claim 1.
7. The compound of claim 6, wherein Ar has the structure of formula IV.
8. The compound of claim 6, wherein Ar has the structure of formula V.
9. A compound according to claim 1 or 6, wherein R is3And R4Each independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted phenanthryl;
preferably, said R is3And R4Each independently selected from one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, pyridyl and phenanthryl.
10. The compound of claim 1, wherein L is1One selected from the group consisting of a single bond, phenylene, pyridylene, pyridine-substituted phenylene, and cyano-substituted phenylene, preferably a single bond or phenylene.
11. The compound of claim 1, wherein L is2One selected from phenylene, naphthylene, pyridine substituted phenylene and cyano substituted phenylene, preferably phenylene.
12. The compound of claim 1, wherein the compound has the structure shown in P1-P80:
13. use of a compound according to any one of claims 1 to 12 in an organic electroluminescent device;
preferably, the compound is used as a material of a light emitting layer of the organic electroluminescent device, preferably as a host material of the light emitting layer.
14. An organic electroluminescent device comprising a substrate, a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one compound according to any one of claims 1 to 12;
preferably, the organic layer comprises a light-emitting layer containing at least one compound according to any one of claims 1 to 12;
preferably, the compound serves as a host material of the light-emitting layer.
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| CN109956876A (en) * | 2017-12-26 | 2019-07-02 | 机光科技股份有限公司 | Organic compound and the organic electroluminescent element for using it |
| CN110386923A (en) * | 2018-04-19 | 2019-10-29 | 北京鼎材科技有限公司 | Carbazole compound and its application and organic electroluminescence device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109956876A (en) * | 2017-12-26 | 2019-07-02 | 机光科技股份有限公司 | Organic compound and the organic electroluminescent element for using it |
| CN110386923A (en) * | 2018-04-19 | 2019-10-29 | 北京鼎材科技有限公司 | Carbazole compound and its application and organic electroluminescence device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115872983A (en) * | 2022-12-27 | 2023-03-31 | 西安欧得光电材料有限公司 | Compound, preparation and application methods thereof and organic electroluminescent device |
| CN115872983B (en) * | 2022-12-27 | 2023-08-18 | 西安欧得光电材料有限公司 | Compound, preparation and application methods and organic electroluminescent device |
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