CN112521374A - Novel organic material and application thereof - Google Patents

Novel organic material and application thereof Download PDF

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CN112521374A
CN112521374A CN202011497175.XA CN202011497175A CN112521374A CN 112521374 A CN112521374 A CN 112521374A CN 202011497175 A CN202011497175 A CN 202011497175A CN 112521374 A CN112521374 A CN 112521374A
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organic material
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梁现丽
刘阳
范洪涛
陈婷
杭德余
段陆萌
曹占广
班全志
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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Abstract

The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic material and application thereof. The novel organic material has a structural formula shown in a formula (I), can be used as an electron transport material, has good thermal stability, can be well applied to OLED devices, and shows low driving voltage and high luminous efficiency.

Description

Novel organic material and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic material and application thereof.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self-luminescence, lightness, thinness, power saving, full curing, wide viewing angle, rich colors and the like, compared with a liquid crystal display device, the OLED does not need a backlight source, has wider viewing angle and low power consumption, and has the response speed 1000 times that of the liquid crystal display device, so the OLED has wider application prospect.
At present, the commonly used electron transport materials such as AlQ3 have low electron mobility, so that the working voltage of the device is higher, and the power consumption is serious; some electron transport materials such as LG201 are not high in triplet level, and when a phosphorescent light emitting material is used as a light emitting layer, an exciton blocking layer needs to be added, otherwise efficiency is reduced, and some materials such as Bephen are easily crystallized, resulting in a reduction in lifetime. Therefore, the stable and efficient electron transport material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the method has important practical application value.
Disclosure of Invention
The invention aims to provide a novel OLED electron transport material with low driving voltage and high luminous efficiency.
In order to develop materials with the properties, the inventor designs a novel benzindolone heterocyclic structure compound, the parent nucleus of the series of compounds has strong electron withdrawing capability, is connected with an electron withdrawing group, can be used as an electron transmission material, has good thermal stability, can be well applied to OLED devices, and can achieve the purpose. Namely, the present invention provides a novel organic material having a structure represented by general formula (i):
Figure BDA0002842523450000021
in the general formula (I), L1And L2Each independently represents a single bond, a substituted or unsubstituted arylene group having C6-C30, a substituted or unsubstituted heteroarylene group having C3-C30;
R1、R2each independently represents a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring, and at least one group is a substituted or unsubstituted hetero atom-containing aromatic group having electron withdrawing properties, which is linked to the parent nucleus represented by the general formula (I) through a C atom; r1、R2May be the same or different;
n is an integer of 1-8;
the substituted or unsubstituted heteroatom-containing and electron-withdrawing aromatic group contains at least one heteroatom; the heteroatom is optionally selected from the group consisting of N atoms, S atoms, and O atoms. The substituted or unsubstituted aromatic group containing hetero atoms and having electron withdrawing property may be monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon; the polycyclic aromatic hydrocarbon can be poly-benzene aliphatic hydrocarbon, biphenyl polycyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon.
The substituted or unsubstituted heteroatom-containing and electron-withdrawing aromatic group may contain no five-membered ring or at least one five-membered ring.
The term "substituted or unsubstituted" means that the substituent is substituted or unsubstituted with 1 or more substituents selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C60 cycloalkyl group, a C3-C60 cycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthioether group and a C2-C60 heteroaryl group, or is linked with 2 or more substituents among the above-exemplified substituents.
As a preferred embodiment of the present invention, L is1And L2Represents a single bond.
In a preferred embodiment of the present invention, n is 1 or 2.
As a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains one heteroatom, specifically, an N atom, an S atom or an O atom. The heteroatoms may be in the five-membered ring or in the benzene ring.
In a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains two heteroatoms, and the two heteroatoms may be the same or different. Specifically, the two heteroatoms are both N atoms, or both S atoms, or both O atoms, or both N atoms and S atoms, or both N atoms and O atoms, or both S atoms and O atoms. The two heteroatoms may be on the same five-membered ring, may be on two different five-membered rings, may be on the same benzene ring, may be on two different benzene rings, or may be one on the five-membered ring and the other on the benzene ring.
In a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains three heteroatoms, and the three heteroatoms may be the same, two of the heteroatoms may be the same, or may be different. Specifically, the three heteroatoms are all N atoms, or all S atoms, or all O atoms, or two N atoms and the other S atom, or two N atoms and the other O atom, or two S atoms and the other N atom, or two S atoms and the other O atom, or two O atoms and the other N atom, or two O atoms and the other S atom, or N atom, S atom and O atom, respectively. The three heteroatoms can be all on the same five-membered ring, can be all on the same benzene ring, can be any two of the other on the same five-membered ring on another five-membered ring, can be any two of the other on the same five-membered ring on a benzene ring, can be any two of the other on the same benzene ring on a five-membered ring, can be any two of the other on the same benzene ring on another benzene ring, can be any two of the other on different five-membered rings on a benzene ring, can be any two of the other on different benzene rings on five-membered rings, can be respectively on three different five-membered rings, or can be respectively on three different benzene rings.
As a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is selected from: substituted or unsubstituted benzodiazine group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted benzoxazolyl group or naphthoxazolyl group, substituted or unsubstituted benzothiazolyl group or naphthothiazolyl group, substituted or unsubstituted benzimidazolyl group or naphthoimidazolyl group, one or more pyridyl-substituted aromatic groups containing at least one benzene ring, substituted or unsubstituted pyridyl group, substituted or unsubstituted bipyridyl group, substituted or unsubstituted phenanthroline group, substituted or unsubstituted benzophenanthroline group, substituted or unsubstituted pyridophenanthroline group, substituted or unsubstituted pyrrolophenanthroline group, substituted or unsubstituted pyrazolophenanthroline group, Substituted or unsubstituted diazino-phenanthrolinyl, one or more triazinyl-substituted aromatic groups containing at least one benzene ring, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl; wherein the diazine may be a pyridazine, a pyrimidine or a pyrazine.
In a preferred embodiment of the present invention, in the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property, the substituent used for substitution may be arbitrarily selected from: alkyl (such as C1-C5 alkyl), phenyl, alkylphenyl, naphthyl, biphenyl, benzo, naphtho, pyridyl, pyrrolyl, imidazolyl, pyrazolyl, diazinyl, quinolyl, isoquinolyl, fluorenyl, oxyfluorenyl, thiofluorenyl, carbazolyl. The number of the substituents is selected from an integer of 1 to 5, preferably 1 to 3. The substitution position of the substituent may be on a carbon atom or on a hetero atom.
As a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is selected from:
Figure BDA0002842523450000041
Figure BDA0002842523450000051
Figure BDA0002842523450000061
Figure BDA0002842523450000071
more preferably, the substituted or unsubstituted heteroatom-containing aromatic group having electron withdrawing properties is selected from:
Figure BDA0002842523450000072
Figure BDA0002842523450000081
further preferably, the substituted or unsubstituted heteroatom-containing aromatic group having electron withdrawing properties is selected from:
Figure BDA0002842523450000082
Figure BDA0002842523450000091
preferably, the novel organic material is selected from the group consisting of compounds represented by the following general formulae I-1 to I-52:
Figure BDA0002842523450000092
Figure BDA0002842523450000101
Figure BDA0002842523450000111
in another preferred embodiment, the novel organic material has a structure represented by general formula (II):
Figure BDA0002842523450000112
in the general formula (II), R3、R4、R5Each independently selected from C6-C18 aryl or C5-C18 heteroaryl; further preferably, R is3And R4The same is true.
The term "aryl" refers to a monocyclic, bicyclic or polycyclic group consisting of the indicated number of carbon atoms, wherein at least one ring has a completely conjugated pi-electron system and conforms to the N +2 rule, i.e. is aromatic, but the entire group need not be completely conjugated. E.g. C6Aryl means phenyl. Aryl groups may also be present as arylene groups, i.e., there are two or more points of attachment to other groups in the aryl structure. Aryl groups in the present invention include, but are not limited to: phenyl, naphthyl, indenyl, indanyl, tetralin, and the like. One or all of the hydrogen atoms in the aryl group may be substituted by: alkyl, cycloalkyl, heteroaryl, heteroalicyclic, halogen, amino, hydroxy, cyano, nitro, carboxy, mercapto, oxy (oxo), alkoxy, aryloxy, alkylmercapto, arylmercapto, carbonyl, thiocarbonyl, C-amide, N-amide, O-aminocarbonyloxy, N-aminocarbonyloxy, O-thiocarbamoyloxy, N-thiocarbamoyloxy, C-ester, O-ester and-NRaRbWherein R isaAnd RbAre respectively selected from: hydrogen, alkyl, cycloalkyl, aryl, acetyl, carbonyl, sulfonyl, trifluoromethanesulfonyl, and the like, and RaAnd RbTogether with the nitrogen atom, may form a 5-or 6-membered heteroalicyclic ring.
The term "heteroaryl" refers to a monocyclic, bicyclic or polycyclic group consisting of the indicated number of non-hydrogen ring atoms, wherein at least one ring atom is a heteroatom selected from O, N, S or P and the remaining ring atoms are carbon atoms, and wherein at least one ring has a completely conjugated pi-electron system and conforms to the N +2 rule, i.e. has aromaticity, but the entire group need not be completely conjugated, e.g. C5Heteroaryl means an aromatic cyclic group consisting of 5 non-hydrogen ring atoms, of which at leastOne ring atom is selected from O, N, S or P, and the remaining ring atoms are carbon atoms. Heteroaryl groups may also occur as heteroarylene groups, i.e., heteroaryl structures having two or more points of attachment to other groups. Heteroaryl groups in the present invention include, but are not limited to: pyridine, pyridinone, tetrahydropyridinone, imidazoie, pyrazine, pyridazine, imidazole, thiazole, thiophene, furan, indole, azaindole, benzimidazole, indoline, indolone, quinuclidine, and the like. One or all of the hydrogen atoms in the heteroaryl group may be substituted by: alkyl, cycloalkyl, aryl, heteroalicyclic, halogen, amino, hydroxy, cyano, nitro, carboxy, mercapto, oxy (oxo), alkoxy, aryloxy, alkylmercapto, arylmercapto, carbonyl, thiocarbonyl, C-amido, N-amido, O-aminocarbonyloxy, N-aminocarbonyloxy, O-thiocarbamoyloxy, N-thiocarbamoyloxy, C-ester, O-ester and-NRaRbWherein R isaAnd RbAre independently selected from hydrogen, alkyl, cycloalkyl, aryl, acetyl, carbonyl, sulfonyl, trifluoromethanesulfonyl, and the like, and RaAnd RbTogether with the nitrogen atom, may form a 5-or 6-membered heteroalicyclic ring.
The novel organic compound takes a benzindolone heterocyclic structure as a parent nucleus, the parent nucleus structure has strong electron-withdrawing capability and good thermal stability, and the structure has proper HOMO and LUMO energy levels and Eg; further, by introducing an electron-withdrawing group into the structure, the electron injection capability can be effectively enhanced, the electron transmission performance is improved, the organic light-emitting diode (OLED) can be well applied to OLED devices and used as an electron transmission material, and the photoelectric performance of the devices can be effectively improved.
The present invention further provides the use of the above novel organic compounds in an organic electroluminescent device, a display device or a lighting device. The organic compound is preferably used as an electron transport material of an electron transport layer in an organic electroluminescent device. The thickness of the electron transport layer can be 10-50 nm, and preferably 20-40 nm.
As a preferred embodiment of the present invention, the organic electroluminescent device sequentially includes, from bottom to top, a transparent substrate, an anode layer, a hole transport layer, an electroluminescent layer, an electron transport layer (including the above novel organic material), an electron injection layer, and a cathode layer.
The novel OLED material provided by the invention takes a benzindolone heterocyclic structure compound as a parent nucleus, the parent nucleus structure has strong electron withdrawing capability, and an electron withdrawing group is introduced into the parent nucleus structure to obtain the novel OLED material. The material has high electron transport performance, good film stability and proper molecular energy level, can be applied to the field of organic electroluminescence, can be used as an electron transport material, and can effectively improve the photoelectric performance of devices. The organic electroluminescent device can be applied to the field of display or illumination.
Detailed Description
The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.
According to the preparation method provided by the present invention, a person skilled in the art can use known common means to implement, such as further selecting a suitable catalyst and a suitable solvent, and determining a suitable reaction temperature, a suitable reaction time, a suitable material ratio, and the like, which are not particularly limited in the present invention. If not specifically stated, the starting materials for the preparation of solvents, catalysts, bases, etc. may be obtained by published commercial routes or by methods known in the art.
The synthesis method of the present invention is briefly described below.
(1) When R1 is the same as R2, the synthetic route is as follows:
Figure BDA0002842523450000131
(2) when R1 is different from R2, the synthetic pathway is as follows (Cl and Br are adjusted as required):
Figure BDA0002842523450000132
EXAMPLE 1 Synthesis of Compound I-1
Figure BDA0002842523450000133
The synthetic route is as follows:
Figure BDA0002842523450000134
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M1(37.5g, 0.1mol), (4-phenylquinazolin-2-yl) boronic acid (50.0g, 0.2mol), cesium carbonate (78g, 0.24mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 60.8g pale yellow solid with yield about 85%.
Product MS (m/e): 715.24, respectively; elemental analysis (C)50H29N5O): theoretical value C: 83.90%, H: 4.08%, N: 9.78 percent; found value C: 83.95%, H: 4.13%, N: 9.62 percent.
EXAMPLE 2 Synthesis of Compound I-12
Figure BDA0002842523450000141
The synthetic route is as follows:
Figure BDA0002842523450000142
into a 1L three-necked flask, M2(51.9g, 0.1mol), 2-naphthylboronic acid (17.2g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen3)4(11.5g, 10 mmol). Heating reflux reaction (temperature in the system)About 78 ℃ C.) for 3 hours, the reaction was stopped. The solvent was evaporated off, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, chromatographed on petroleum ether/ethyl acetate (2:1), the solvent was dried by spinning, slurried with ethyl acetate, filtered to give 49.9g of pale yellow solid I-12-1 with a yield of about 88%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-12-1(56.7g, 0.1mol), benzo [ d ] thiazol-2-ylboronic acid (17.9g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 53.9g of pale yellow solid with the yield of about 81%.
Product MS (m/e): 666.18, respectively; elemental analysis (C)47H26N2OS): theoretical value C: 84.66%, H: 3.93%, N: 4.20 percent; found value C: 84.70%, H: 3.99%, N: 4.06 percent.
EXAMPLE 3 Synthesis of Compound I-18
Figure BDA0002842523450000151
The synthetic route is as follows:
Figure BDA0002842523450000152
into a 1L three-necked flask, M3(34.3g, 0.1mol), (4'- (methyl-d 3) - [1,1' -biphenyl) was charged]-3-yl) boronic acid (21.5g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, water 150mL, the reaction system was purged with nitrogen and Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. Distilling off solvent, extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, performing petroleum ether/ethyl acetate (2:1) column chromatography, spin-drying solvent, pulping with ethyl acetate, and filtering to obtain 28.6g pale yellow extractSolid I-18-1, yield about 66%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-18-1(43.4g, 0.1mol), naphtho [2,3-d ] oxazol-2-ylboronic acid (21.3g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were added in this order, and stirring was started. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 43.7g of pale yellow solid with the yield of about 77%.
Product MS (m/e): 567.20, respectively; elemental analysis (C)40H21D3N2O2): theoretical value C: 84.63%, H: 4.79%, N: 4.93 percent; found value C: 84.69%, H: 4.85%, N: 4.88 percent.
EXAMPLE 4 Synthesis of Compound I-23
Figure BDA0002842523450000161
The synthetic route is as follows:
Figure BDA0002842523450000162
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M4(29.9g, 0.1mol), (3, 5-bis (pyridin-4-yl) phenyl) boronic acid (55.2g, 0.2mol), cesium carbonate (78g, 0.24mol) and dioxane 400ml were added in this order, followed by stirring. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 56.0g pale yellow solid with yield of about 81%.
Product MS (m/e): 691.24, respectively; elemental analysis (C)48H29N5O): theoretical value C: 83.34%, H: 4.23%, N: 10.12 percent; fruit of Chinese wolfberryMeasured value C: 83.39%, H: 4.26%, N: 10.01 percent.
EXAMPLE 5 Synthesis of Compound I-28
Figure BDA0002842523450000163
The synthetic route is as follows:
Figure BDA0002842523450000171
into a 1L three-necked flask, M5(41.9g, 0.1mol), (1, 10-phenanthrolin-5-yl) boronic acid (22.4g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, and filtration is carried out to obtain 35.8g of light yellow solid I-28-1 with the yield being about 69%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-28-1(51.9g, 0.1mol), dibenzo [ b, d ] thiophen-3-ylboronic acid (22.8g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane (400 ml) were added in this order, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 56.0g of pale yellow solid with the yield of about 84%.
Product MS (m/e): 667.17, respectively; elemental analysis (C)46H25N3OS): theoretical value C: 82.74%, H: 3.77%, N: 6.29 percent; found value C: 82.79%, H: 3.83%, N: 6.16 percent.
EXAMPLE 6 Synthesis of Compound I-31
Figure BDA0002842523450000172
The synthetic route is as follows:
Figure BDA0002842523450000181
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M6(37.5g, 0.1mol), (4, 6-diphenyl-1, 3, 5-triazin-2-yl) boronic acid (55.4g, 0.2mol), cesium carbonate (78g, 0.24mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 58.4g of pale yellow solid with the yield of about 76%.
Product MS (m/e): 769.26, respectively; elemental analysis (C)52H31N7O): theoretical value C: 81.13%, H: 4.06%, N: 12.74 percent; found value C: 81.18%, H: 4.11%, N: 12.63 percent.
EXAMPLE 7 Synthesis of Compound I-39
Figure BDA0002842523450000182
The synthetic route is as follows:
Figure BDA0002842523450000191
into a 1L three-necked flask, M7(41.9g, 0.1mol), (4, 6-bis (9, 9-dimethyl-9H-fluoren-2-yl) -1,3, 5-triazin-2-yl) boronic acid (50.9g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and after the reaction system was purged with nitrogen, Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. Reducing the evaporation of the solvent, and extracting by dichloromethaneDrying with anhydrous magnesium sulfate, filtering, performing petroleum ether/ethyl acetate (2:1) column chromatography, spin-drying the solvent, pulping with ethyl acetate, and filtering to obtain 51.5g of pale yellow solid I-39-1 with the yield of about 64%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-39-1(80.4g, 0.1mol), 2-naphthylboronic acid (17.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and 400ml dioxane were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 70.8g of pale yellow solid with the yield of about 79%.
Product MS (m/e): 896.35, respectively; elemental analysis (C)65H44N4O): theoretical value C: 87.03%, H: 4.94%, N: 6.25 percent; found value C: 87.08%, H: 4.99%, N: 6.13 percent.
EXAMPLE 8 Synthesis of Compound I-43
Figure BDA0002842523450000201
The synthetic route is as follows:
Figure BDA0002842523450000202
into a 1L three-necked flask, M8(41.9g, 0.1mol), (4, 6-bis (quinolin-3-yl) -1,3, 5-triazin-2-yl) boronic acid (39.2g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and after the reaction system was purged with nitrogen, Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, and filtration is carried out to obtain 47.2g of light yellow solid I-43-1 with the yield of about 70%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-43-1(67.4g, 0.1mol), dibenzo [ b, d ] furan-3-ylboronic acid (21.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 66.1g pale yellow solid with yield about 82%.
Product MS (m/e): 806.24, respectively; elemental analysis (C)55H30N6O2): theoretical value C: 81.87%, H: 3.75%, N: 10.42 percent; found value C: 81.92%, H: 3.70%, N: 10.39 percent.
EXAMPLE 9 Synthesis of Compound I-46
Figure BDA0002842523450000211
The synthetic route is as follows:
Figure BDA0002842523450000212
m9(41.9g, 0.1mol), 9' -spirobis [ fluorene ] were added to a 1L three-necked flask]-2-yl boronic acid (36.0g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, water 150mL, the reaction system was purged with nitrogen and Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, and 53.7g of light yellow solid I-46-1 is obtained after filtration, and the yield is about 82%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-46-1(65.5g, 0.1mol), (6-isopropylquinolin-2-yl) boronic acid (21.5g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane (400 ml) were added in this order, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 65.6g of pale yellow solid with the yield of about 83%.
Product MS (m/e): 790.30, respectively; elemental analysis (C)59H38N2O): theoretical value C: 89.59%, H: 4.84%, N: 3.54 percent; found value C: 89.65%, H: 4.90%, N: 3.40 percent.
EXAMPLE 10 Synthesis of Compound I-50
Figure BDA0002842523450000221
The synthetic route is as follows:
Figure BDA0002842523450000222
m10(41.9g, 0.1mol), (4- (dibenzo [ b, d ]) was put into a 1L three-necked flask]Furan-3-yl) -6-phenyl-1, 3, 5-triazin-2-yl boronic acid (36.7g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, water 150mL, the reaction system was purged with nitrogen and then Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, 51.6g of light yellow solid I-50-1 is obtained after filtration, and the yield is about 78%.
A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-50-1(66.2g, 0.1mol), benzo [ d ] thiazol-2-ylboronic acid (17.9g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 63.2g of pale yellow solid with the yield of about 83%.
Product MS (m/e): 761.19, respectively; elemental analysis (C)50H27N5O2S): theoretical value C: 78.83%, H: 3.57%, N: 9.19 percent; found value C: 78.88%, H: 3.62%, N: 9.06 percent.
According to the technical schemes of the examples 1 to 10, other compounds of I-1 to I-52 can be synthesized only by simply replacing corresponding raw materials and not changing any substantial operation.
Device examples Using the Compounds of the invention as Electron transport materials
The embodiment provides a group of OLED green light devices OLED-1, and the structures of the devices are as follows:
ITO/HATCN(1nm)/HT01(40nm)/NPB(20nm)/EML(30nm)/I-1(40nm)/LiF(1nm)/Al。
the molecular structure of each functional layer material is as follows:
Figure BDA0002842523450000231
(1) ultrasonically cleaning a glass substrate coated with an ITO transparent conductive film in cleaning solution, ultrasonically treating the glass substrate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solution (volume ratio is 1: 1), baking the glass substrate in a clean environment until the water is completely removed, carrying out etching and ozone treatment by using an ultraviolet lamp, and bombarding the surface by using low-energy cation beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then evaporating a hole transport layer NPB with the evaporation rate of 0.1nm/s and the evaporation film thickness of 20 nm;
(3) vacuum evaporating EML on the hole transport layer as the light emitting layer of the device, the EML including a hostMaterials and dye materials, placing the host material as a luminescent layer in a chamber of a vacuum vapor deposition device by a multi-source co-evaporation method, and adding Ir (ppy) as a dopant3Placing in another chamber of vacuum vapor deposition equipment, and adjusting evaporation rate of main material to 0.1nm/s, Ir (ppy)3The concentration of (2) is 10%, and the total film thickness of evaporation plating is 30 nm;
(4) vacuum evaporating the compound I-1 of the invention on the luminescent layer to form an electron transport layer with the thickness of 40nm, wherein the evaporation rate is 0.1 nm/s;
(5) LiF with the thickness of 1nm is sequentially subjected to vacuum evaporation on the electron transport layer to serve as an electron injection layer, and an Al layer with the thickness of 150nm serves as a cathode of the device.
And (3) respectively obtaining the OLED-2-OLED-10 provided by the invention by respectively replacing I-1 in the step (4) with I-12, I-18, I-23, I-28, I-31, I-39, I-43, I-46 and I-50 according to the same steps.
Following the same procedure as above, only replacing I-1 in step (4) with commercial Bphen (comparative compound) gave comparative example OLED-11 provided by the present invention. The structure of the Bphen is specifically as follows:
Figure BDA0002842523450000241
the performance of the obtained devices OLED-1 to OLED-11 is detected, and the detection results are shown in Table 1.
Table 1: performance test result of OLED device
Figure BDA0002842523450000242
The results show that devices 4, 5 and 9 of devices OLED-1 to OLED-10 prepared by using the organic material shown in formula I provided by the invention are basically consistent with comparative example 11; the current efficiency of the devices 1, 2,3 and 10 is higher, and the working voltage is lower than that of the OLED-11 device taking Bphen as an electron transport material under the condition of the same brightness; while the devices 6, 7, 8 show better performance in terms of operating voltage and current efficiency, with optimum performance. From the above, the organic material provided by the invention can be applied to an OLED device and used as an electron transport material with good performance.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A novel organic material having a structural formula according to formula (I):
Figure FDA0002842523440000011
in the formula:
L1and L2Each independently represents a single bond, a substituted or unsubstituted arylene group having C6-C30, a substituted or unsubstituted heteroarylene group having C3-C30;
R1、R2the same or different, each independently represents a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring; wherein R is1And R2At least one of the groups is a substituted or unsubstituted aromatic group which contains heteroatom and has electron-withdrawing property, and is connected with the mother nucleus shown in the general formula (I) through C atom, wherein the heteroatom is N atom, S atom or O atom;
n is an integer of 1 to 8.
2. The novel organic material according to claim 1, wherein in formula (I), L is1And L2Represents a single bond.
3. A novel organic material according to claim 1 or 2, characterized in that in formula (I), n is 1 or 2.
4. A novel organic material according to any one of claims 1 to 3, characterized in that in formula (I), said substituted or unsubstituted heteroatom-containing aromatic group with electron-withdrawing properties is selected from: substituted or unsubstituted benzodiazine group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted benzoxazolyl group or naphthoxazolyl group, substituted or unsubstituted benzothiazolyl group or naphthothiazolyl group, substituted or unsubstituted benzimidazolyl group or naphthoimidazolyl group, one or more pyridyl-substituted aromatic groups containing at least one benzene ring, substituted or unsubstituted pyridyl group, substituted or unsubstituted bipyridyl group, substituted or unsubstituted phenanthroline group, substituted or unsubstituted benzophenanthroline group, substituted or unsubstituted pyridophenanthroline group, substituted or unsubstituted pyrrolophenanthroline group, substituted or unsubstituted pyrazolophenanthroline group, Substituted or unsubstituted diazino-phenanthrolinyl, one or more triazinyl-substituted aromatic groups containing at least one benzene ring, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl.
5. A novel organic material as claimed in any one of claims 1 to 4, wherein in the formula (I), the substituent group for substitution in the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing property may be selected from the group consisting of: alkyl, phenyl, alkylphenyl, naphthyl, biphenyl, benzo, naphtho, pyridyl, pyrrolyl, imidazolyl, pyrazolyl, diazinyl, quinolyl, isoquinolyl, fluorenyl, oxyfluorenyl, dibenzothiophenyl, carbazolyl; the number of the substituents is selected from an integer of 1 to 5, preferably 1 to 3.
6. A novel organic material according to any one of claims 1 to 3, characterized in that in formula (I), said substituted or unsubstituted heteroatom-containing aromatic group with electron-withdrawing properties is selected from:
Figure FDA0002842523440000021
Figure FDA0002842523440000031
Figure FDA0002842523440000041
7. the novel organic material according to claim 1, wherein the formula (I) is selected from the group consisting of compounds represented by the following general formulae I-1 to I-52:
Figure FDA0002842523440000051
Figure FDA0002842523440000061
Figure FDA0002842523440000071
8. use of the novel organic material as claimed in any of claims 1 to 7 as an electron transport material in an organic electroluminescent device, a display device or a lighting device.
9. An organic electroluminescent device, wherein the electron transport layer of the organic electroluminescent device comprises the novel organic material according to any one of claims 1 to 7, and preferably, the thickness of the electron transport layer is 10 to 50nm, and more preferably 20 to 40 nm.
10. A display device or a lighting device comprising the novel organic material according to any one of claims 1 to 7 or the organic electroluminescent element according to claim 9.
CN202011497175.XA 2020-12-17 2020-12-17 Novel organic material and application thereof Pending CN112521374A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150128590A (en) * 2014-05-08 2015-11-18 롬엔드하스전자재료코리아유한회사 An electron transport material and an organic electroluminescence device comprising the same
CN111423386A (en) * 2020-03-30 2020-07-17 北京燕化集联光电技术有限公司 Novel organic material and application thereof
CN111909171A (en) * 2020-07-31 2020-11-10 北京燕化集联光电技术有限公司 Novel electronic transmission material and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150128590A (en) * 2014-05-08 2015-11-18 롬엔드하스전자재료코리아유한회사 An electron transport material and an organic electroluminescence device comprising the same
CN111423386A (en) * 2020-03-30 2020-07-17 北京燕化集联光电技术有限公司 Novel organic material and application thereof
CN111909171A (en) * 2020-07-31 2020-11-10 北京燕化集联光电技术有限公司 Novel electronic transmission material and application thereof

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