CN112142672B - Anthracene nitrogen-containing organic luminescent compound and preparation method and application thereof - Google Patents
Anthracene nitrogen-containing organic luminescent compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anthracene nitrogen-containing organic luminescent compound and a preparation method and application thereof, wherein the specific structure of the anthracene nitrogen-containing organic luminescent compound is shown as a general formula 1 in the specification, and the preparation method comprises the following steps: taking toluene as a solvent, reacting a raw material A with a raw material B in the presence of sodium tert-butoxide, tris (dibenzylideneacetone) dipalladium and tris (tert-butyl) phosphorus to obtain an intermediate product C, then taking dichloromethane as a solvent, reacting the intermediate product C with NBS to obtain an intermediate product D, and taking a mixed solution of toluene, ethanol and water as a solvent, reacting the intermediate product D with the raw material E in the presence of potassium carbonate and tetrakis (triphenylphosphine) palladium to finally obtain the compound shown in the general formula I. The anthracene derivative provided by the invention has high electron transport performance, and can improve the electron transport efficiency of the device and prolong the service life of the device when being applied to an organic electroluminescent device. In addition, the preparation method provided by the invention is simple and easy to operate, and is suitable for industrial popularization.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to an anthracene nitrogen-containing organic luminescent compound and a preparation method and application thereof.
Background
The organic electroluminescent technology can be used for manufacturing novel display products and novel illumination products, has wide application prospect, and is expected to replace the existing liquid crystal display and fluorescent lamp illumination. The OLED light-emitting device is composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer, wherein the Hole Transport Layer (HTL) is responsible for adjusting the injection speed and the injection amount of holes, and the Electron Transport Layer (ETL) is responsible for adjusting the injection speed and the injection amount of electrons.
In addition, the electron transport material constituting the electron transport layer should satisfy the following requirements: (1) the material has good electron transmission characteristics, namely, high electron mobility; (2) the cathode has higher electron affinity and is easy to inject electrons from the cathode; (3) the relatively high ionization energy is favorable for blocking holes; (4) the ability to form an exciplex with the light-emitting layer; (5) good film forming property and thermal stability, and difficult crystallization. In the prior art, the hole mobility of the hole transport material in the OLED device is generally much greater than the electron mobility of the electron transport material, but the carrier transport rate imbalance causes significant degradation of the device performance. Thus, has better electron mobility, and can effectively transport electrons to recombination regions far away from the cathode. Tris (8-hydroxyquinoline) aluminum (Alq)3) Although the electron transport material has been used for nearly 30 years since the invention, many data prove that the electron transport material is superior to conventional materials, the application of the electron transport material is limited by factors such as movement to other layers.
In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device.
Therefore, how to provide an organic electroluminescent material capable of realizing high efficiency, long lifetime and low voltage of an organic light emitting device is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides an anthracene-based nitrogen-containing organic light-emitting compound with a simple preparation method, which has good electron transport properties, and also has good thermal stability and chemical stability.
In addition, the invention also provides an organic electroluminescent device comprising the anthracene nitrogen-containing organic luminescent compound and application of the organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
an anthracene nitrogen-containing organic light-emitting compound having the following structure:
wherein, R is1-R3Each independently selected from substituted or unsubstituted C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, substituted or unsubstituted C1-C30Alkoxy, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C60Condensed ring group of (5) or substituted or unsubstituted C10-C60Said R is spirocyclic1-R3Monocyclic ring, C, each independently linked to an adjacent substituent3-C30Aliphatic ring or C6-C30An aromatic ring;
said L1、L2Each independently selected from the group consisting of a bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C60A fused ring group;
each ring A, Ar is independently selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl;
the heteroaryl group is monocyclic, C3-C30Cycloalkyl or 3-10 membered heterocycloalkyl.
Preferably, said R is1-R3Wherein at least one carbon atom is replaced by one or more of nitrogen, oxygen and sulfur.
Preferably, at least one carbon atom in the heteroaryl group is replaced by one or more of nitrogen, oxygen and sulfur.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more of the above-shown substituents are bonded, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
The beneficial effects of the above technical scheme are: the compound of the invention takes the anthracene derivative as a mother nucleus and is connected with the nitrogen-containing heterocycle, thus destroying the molecular symmetry, avoiding the aggregation effect among molecules and having the characteristics of difficult crystallization and aggregation among molecules and good film-forming property. The compound contains at least 2N atoms, and the N atoms have good electron transport performance, so that the compound provided by the invention has good electron transport performance, and the luminescence performance is greatly improved. N atoms can also influence the HOMO energy level, LUMO energy level and triplet state energy level distribution of the material, the material with deeper HOMO energy level and slightly lower T1 energy level can be used as a hole blocking layer/electron transport layer material, the material with shallower HOMO energy level and higher T1 energy level can be used as a main body material of a bias electron type light-emitting layer, and simultaneously the Bond Dissociation Energy (BDE) of the compound is improved due to the electron-withdrawing property of the N atoms, so that the thermal stability and the chemical stability of the material are improved, and the service life of the device can be greatly prolonged when the material is applied to an organic electroluminescence device. When the anthracene nitrogen-containing organic light-emitting compound is applied to an OLED device, the stability of a film formed by the material can be kept, the service life of the OLED device is prolonged, and the anthracene nitrogen-containing organic light-emitting compound has a good application effect in the OLED light-emitting device and a good industrial prospect.
In some other embodiments of the present invention, the organic light emitting compound of formula I has the following specific structure:
a preparation method of an anthracene nitrogen-containing organic luminescent compound comprises the following steps:
1) dissolving a raw material A, a raw material B and sodium tert-butoxide in toluene under the protection of inert gas to obtain a mixture 1;
2) adding tris (dibenzylideneacetone) dipalladium and tris (tert-butyl) phosphorus into the mixture 1, and carrying out reflux stirring reaction for 12 hours at the temperature of 100 ℃ and 120 ℃ to obtain a mixture 2;
3) removing impurities from the mixture 2, washing, extracting, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, concentrating and purifying to obtain an intermediate product C;
4) under the condition of room temperature, adding NBS into a dichloromethane solution of an intermediate product C for reaction, after the reaction is finished, concentrating the reaction solution, and then dropwise adding the concentrated solution into petroleum ether stirred at the speed of 300-1000rpm under the condition of room temperature to precipitate solids; after the solid is completely separated out, carrying out suction filtration and drying for 10-16h at 50-80 ℃ to obtain an intermediate product D;
5) adding the intermediate product D, the raw material E and potassium carbonate into a mixed solvent of toluene, ethanol and water, adding tetrakis (triphenylphosphine) palladium under the protection of inert gas, heating to 100-120 ℃, and reacting for 7-9h to obtain a compound shown in the general formula I;
the synthetic route of the general formula I is as follows:
preferably, the equivalent ratio of the raw material A, the raw material B and the sodium tert-butoxide in the step 1) is (0.8-1.2): (1.0-1.2): (2.8-3.2), and the volume ratio of the toluene to the raw material A is 1: (2-8).
Preferably, the impurity removal in the step 3) uses diatomite to remove salt and catalyst, and the washing is as follows: adding water for washing, wherein the extraction is that the organic phase is extracted by dichloromethane; the concentration is reduced pressure concentration; the purification is a purification of the concentrated product using column chromatography.
Preferably, the volume ratio of the dichloromethane to the product C in step 4) is 1: (3-6); the equivalent ratio of NBS to intermediate C is (1.0-1.2) to 1.0; the stirring speed was 300 and 1000 rpm.
Preferably, the volume ratio of the toluene, the ethanol and the water in the step 5) is (2-4): (0.8-1.2).
By adopting the preparation method to prepare the general formula 1, the product in the invention has faster generation rate and higher purity.
An organic electroluminescent device comprising: the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer comprises a light-emitting layer and an electron transmission layer, and the electron transmission layer is an anthracene nitrogen-containing organic light-emitting compound.
The device prepared by adopting the multi-functional layer can be obviously improved in performance, the driving voltage is reduced, and the luminous efficiency of the device is improved.
An organic electroluminescent device is applied to an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
According to the technical scheme, compared with the prior art, the invention discloses and provides an anthracene nitrogen-containing organic luminescent compound and a preparation method and application thereof. The invention has the following beneficial effects:
(1) the anthracene nitrogen-containing organic luminescent compound provided by the invention has good electron transport performance, and can greatly improve the luminescent performance of an organic electroluminescent device;
(2) the anthracene nitrogen-containing organic luminescent compound provided by the invention has excellent thermal stability and chemical stability, and can prolong the service life of an organic electroluminescent device;
(3) the preparation method provided by the invention is simple and easy to operate, can obtain a product with higher purity, and is convenient for industrial production and popularization.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses an anthracene nitrogen-containing organic light-emitting compound, which has the following structure:
wherein R is1-R3Each independently selected from substituted or unsubstituted C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, substituted or unsubstituted C1-C30Alkoxy, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C60Condensed ring group of (5) or substituted or unsubstituted C10-C60Spiro radical of (A), R1-R3Monocyclic ring, C, each independently linked to an adjacent substituent3-C30Aliphatic ring or C6-C30An aromatic ring;
L1、L2each independently selected from the group consisting of a bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C60A fused ring group;
each ring A, Ar is independently selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted 3-30 membered heteroaryl;
heteroaryl is monocyclic, C3-C30Cycloalkyl or 3-10 membered heterocycloalkyl.
To further optimize the technical solution of the present invention, R1-R3Wherein at least one carbon atom is replaced by one or more of nitrogen, oxygen and sulfur.
Further, at least one carbon atom in the heteroaryl group is replaced by one or more of nitrogen, oxygen and sulfur.
The embodiment of the invention also provides a preparation method of the anthracene nitrogen-containing organic luminescent compound, which is characterized by comprising the following steps:
1) dissolving a raw material A, a raw material B and sodium tert-butoxide in toluene under the protection of inert gas to obtain a mixture 1;
2) adding tris (dibenzylideneacetone) dipalladium and tris (tert-butyl) phosphorus into the mixture 1, and carrying out reflux stirring reaction for 12 hours at the temperature of 100 ℃ and 120 ℃ to obtain a mixture 2;
3) removing impurities from the mixture 2, washing, extracting, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, concentrating and purifying to obtain an intermediate product C;
4) under the condition of room temperature, adding NBS into a dichloromethane solution of an intermediate product C for reaction, after the reaction is finished, concentrating the reaction solution, and then dropwise adding the concentrated solution into petroleum ether stirred at the speed of 300-1000rpm under the condition of room temperature to precipitate solids; after the solid is completely separated out, carrying out suction filtration and drying for 10-16h at 50-80 ℃ to obtain an intermediate product D;
5) adding the intermediate product D, the raw material E and potassium carbonate into a mixed solvent of toluene, ethanol and water, adding tetrakis (triphenylphosphine) palladium under the protection of inert gas, heating to 100-120 ℃, and reacting for 7-9h to obtain a compound shown in the general formula I;
the synthetic route of the general formula I is as follows:
in order to further optimize the technical scheme, the equivalent ratio of the raw material A, the raw material B and the sodium tert-butoxide in the step 1) is (0.8-1.2) to (1.0-1.2) to (2.8-3.2), and the volume ratio of the toluene to the raw material A is 1: (2-8).
Further, in the step 3), salt and catalyst are removed by using diatomite, and washing is as follows: washing with water, and extracting the organic phase with dichloromethane; concentrating under reduced pressure; purification the concentrated product was purified using column chromatography.
Further, the volume ratio of the dichloromethane to the product C in the step 4) is 1: (3-6); the equivalent ratio of NBS to intermediate C is (1.0-1.2) to 1.0; the stirring speed was 300 and 1000 rpm.
Further, the volume ratio of the toluene, the ethanol and the water in the step 5) is (2-4): (0.8-1.2): (0.8-1.2).
The embodiment of the invention also discloses an organic electroluminescent device, which comprises: the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer comprises a light-emitting layer and an electron transmission layer, and the electron transmission layer is an anthracene nitrogen-containing organic light-emitting compound.
The embodiment of the invention also discloses application of the organic electroluminescent device in an organic luminescent device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
Example 1
The preparation method of the anthracene nitrogen-containing organic luminescent compound (compound 1) comprises the following specific synthetic steps:
1) under nitrogen protection, raw material A-1(50mmol), raw material B-1(55mmol) and sodium tert-butoxide (150mmol) were placed in a flask and dissolved in dry toluene (200 mL). Then, Pd is added2(dba)3(0.56mmol) and P (t-Bu)3(2.8mmol) was added to the above reaction mixture, heated to 110 ℃ and refluxed with stirring for 12 hours. After the reaction, the salts and the catalyst were removed using celite, washed with water and the organic phase was extracted with dichloromethane. The organic phases were combined, and the extracted product was dried over anhydrous magnesium sulfate and filtered. Then, the filtered product was concentrated under reduced pressure. And the solvent was removed using a rotary evaporator. Intermediate C-1(23.3g, 85% yield, Ms:549.22) was obtained.
2) Intermediate C-1(40mmol) was added to dichloromethane (150mL) and NBS (44mmol) was added. The mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. After the reaction, the reaction solution was concentrated to a small amount and added dropwise to petroleum ether under stirring. After the solid was completely precipitated, it was filtered off with suction and dried to give intermediate D-1(22.6g, yield 90%, Ms: 627.13).
3)N2Under protection, respectively adding the intermediate D-1(30mmol), the reactant E-1(36mmol), tetrakis (triphenylphosphine) palladium (0.3mmol) and potassium carbonate (60mmol) into a mixed solvent of toluene (120mL), ethanol (40mL) and water (40mL), heating to 110 ℃, refluxing for reaction for 8h, cooling to room temperature after the reaction is finished, after solid precipitation is finished, performing suction filtration, and then using waterWashing to remove the salt, rinsing with ethanol, drying the filter cake, and purifying the remaining substance by column chromatography, wherein the eluent has a volume ratio of dichloromethane: petroleum ether 1:6 gave compound 1(17.0g, 81% yield).
Compound 1: 701.28 mass spectrum theoretical value; 701.55 mass spectrum test value.
Example 2
The preparation method of the anthracene nitrogen-containing organic luminescent compound (compound 20) comprises the following specific synthetic steps:
1) under nitrogen protection, raw material A-20(50mmol), raw material B-20(55mmol) and sodium tert-butoxide (150mmol) were placed in a flask and dissolved in dry toluene (200 mL). Then, the tripd is added2(dba)3(0.56mmol) and P (t-Bu)3(2.8mmol) was added to the above reaction mixture, warmed to 110 ℃ and then refluxed and stirred for 12 hours. After the reaction, the salts and the catalyst were removed using celite, washed with water and the organic phase was extracted with dichloromethane. The organic phases were combined, the extracted product was dried over anhydrous magnesium sulfate and filtered. Then, the filtered product was concentrated under reduced pressure. And the solvent was removed using a rotary evaporator. Intermediate C-20(25.6g, 82% yield, Ms:624.79) was obtained.
2) Intermediate C-1(40mmol) was added to dichloromethane (150mL) and NBS (44mmol) was added. The mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. After the reaction, the reaction solution was concentrated to a small amount and added dropwise to petroleum ether under stirring. After the solid was completely precipitated, it was filtered off with suction and dried to give intermediate D-20(24.8g, yield 88%, Ms: 703.68).
3)N2Under protection, respectively adding the intermediate D-20(30mmol), the reactant E-20(36mmol), tetrakis (triphenylphosphine) palladium (0.3mmol) and potassium carbonate (60mmol) into a mixed solvent of toluene (120mL), ethanol (40mL) and water (40mL), heating to 110 ℃, refluxing for reaction for 8h, cooling to room temperature after the reaction is finished, after solid precipitation is finished, carrying out suction filtration, washing with water to removeEluting with ethanol, drying the filter cake, and purifying the remaining substance by column chromatography, wherein the eluent has the volume ratio of dichloromethane: petroleum ether 1:6 gave compound 20(16.6g, 79% yield).
Compound 20: 700.29 mass spectrum theoretical value; 700.85 mass spectrum test value.
Example 3
The preparation method of the anthracene nitrogen-containing organic luminescent compound (compound 43) comprises the following specific synthetic steps:
1) under nitrogen, starting material A-43(50mmol), starting material B-43(55mmol) and sodium tert-butoxide (150mmol) were placed in a flask and dissolved in dry toluene (200 mL). Then, the tripd is added2(dba)3(0.56mmol) and P (t-Bu)3(2.8mmol) was added to the above reaction mixture, heated to 110 ℃ and refluxed with stirring for 12 hours. After the reaction, the salts and the catalyst were removed using celite, washed with water and the organic phase was extracted with dichloromethane. The organic phases were combined, and the extracted product was dried over anhydrous magnesium sulfate and filtered. Then, the filtered product was concentrated under reduced pressure. And the solvent was removed using a rotary evaporator. Intermediate C-43(20.0g, 84% yield, Ms:474.18) was obtained.
2) Intermediate C-1(40mmol) was added to dichloromethane (150mL) and NBS (44mmol) was added. The mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. After the reaction, the reaction solution was concentrated to a small amount and added dropwise to petroleum ether under stirring. After the solid was completely precipitated, it was filtered off with suction and dried to obtain intermediate D-43(19.0g, yield 86%, Ms: 552.09).
3)N2Under protection, respectively adding the intermediate D-43(30mmol), the reactant E-43(36mmol), tetrakis (triphenylphosphine) palladium (0.3mmol) and potassium carbonate (60mmol) into a mixed solvent of toluene (120mL), ethanol (40mL) and water (40mL), heating to 110 ℃, refluxing and reacting for 8h, cooling to room temperature after reaction is finished, after solid precipitation is finished, carrying out suction filtration, washing with water to remove the salt, leaching with ethanol, and leaching with ethanol to remove the saltThe filter cake was dried and the remaining material was purified by column chromatography eluting with dichloromethane in volume ratio: petroleum ether 1:6 gave compound 43(16.7g, 82% yield).
Compound 43: 677.26 mass spectrum theoretical value; 677.32 mass spectrum test value.
Example 4
The preparation method of the anthracene nitrogen-containing organic luminescent compound (compound 83) comprises the following specific synthetic steps:
1) under nitrogen protection, raw material A-83(50mmol), raw material B-83(55mmol) and sodium tert-butoxide (150mmol) were placed in a flask and dissolved in dry toluene (200 mL). Then, the tripd is added2(dba)3(0.56mmol) and P (t-Bu)3(2.8mmol) was added to the above reaction mixture, heated to 110 ℃ and refluxed with stirring for 12 hours. After the reaction, the salts and the catalyst were removed using celite, washed with water and the organic phase was extracted with dichloromethane. The organic phases were combined, and the extracted product was dried over anhydrous magnesium sulfate and filtered. Then, the filtered product was concentrated under reduced pressure. And the solvent was removed using a rotary evaporator. Intermediate C-83(23.4g, 85% yield, Ms:550.24) was obtained.
2) Intermediate C-1(40mmol) was added to dichloromethane (150mL) and NBS (44mmol) was added. The mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. After the reaction, the reaction solution was concentrated to a small amount and added dropwise to petroleum ether under stirring. After the solid is completely precipitated, the intermediate D-83(22.9g, yield 91%, Ms:628.15) is obtained after suction filtration and drying.
3)N2Under protection, respectively adding the intermediate D-83(30mmol), the reactant E-83(36mmol), tetrakis (triphenylphosphine) palladium (0.3mmol) and potassium carbonate (60mmol) into a mixed solvent of toluene (120mL), ethanol (40mL) and water (40mL), heating to 110 ℃, refluxing and reacting for 8h, cooling to room temperature after reaction is finished, after solid precipitation is finished, carrying out suction filtration, washing with water to remove salt, leaching with ethanol, drying a filter cake, and drying the filter cake with ethanolPurifying the remaining substance by column chromatography, eluting with dichloromethane in a volume ratio: petroleum ether 1:6 gave compound 83(16.7g, 82% yield).
Compound 83: 677.28 mass spectrum theoretical value; 677.36 mass spectrum test value.
Example 5
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 5) differs from the preparation of example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-5 and the raw material B-5 respectively, and heating to 100 ℃ to finally obtain an intermediate C-5;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-5 to finally obtain an intermediate D-5;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-5 and the reactant E-5 respectively, heating to 100 ℃, and reacting for 9 hours to finally obtain the compound 5.
Example 6
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 8) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-8 and the raw material B-8 respectively, and heating to 120 ℃ to finally obtain an intermediate C-8;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-8 to finally obtain an intermediate D-8;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-8 and the reactant E-8 respectively, heating to 120 ℃, and reacting for 7h to finally obtain the compound 8.
Example 7
The preparation of the anthracene nitrogen-containing organic luminescent compound (compound 14) only differs from the preparation of the compound in the following specific synthetic steps from example 1:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-14 and the raw material B-14 respectively to finally obtain an intermediate C-14, wherein the equivalent ratio of the raw material A-14 to the raw material B-14 to sodium tert-butoxide is 0.8:1.0: 2.8;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-14 to finally obtain an intermediate D-14;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-14 and the reactant E-14 respectively to finally obtain the compound 14.
Example 8
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 18) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-18 and the raw material B-18 respectively to finally obtain an intermediate C-18, wherein the equivalent ratio of the raw material A-18 to the raw material B-18 to the sodium tert-butoxide is 1.2: 1.2: 3.2;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-18 to finally obtain an intermediate D-18;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-18 and the reactant E-18 respectively to finally obtain the compound 18.
Example 9
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 29) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with a raw material A-29 and a raw material B-29 respectively to finally obtain an intermediate C-29;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-29 to finally obtain an intermediate D-29;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-29 and the reactant E-29 respectively, wherein the volume ratio of the toluene to the ethanol to the water is 2:0.8:0.8, and finally obtaining the compound 29.
Example 10
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 34) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-34 and the raw material B-34 respectively to finally obtain an intermediate C-34;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-34 to finally obtain an intermediate D-34;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with an intermediate D-34 and a reactant E-34 respectively, wherein the volume ratio of the toluene to the ethanol to the water is 4: 1.2: 1.2, compound 34 is finally obtained.
Example 11
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 40) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-40 and the raw material B-40 respectively to finally obtain an intermediate C-40;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-40, wherein the volume of a dichloromethane solution is 3 times that of the product C-40, and finally obtaining an intermediate D-40;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-40 and the reactant E-40 respectively to finally obtain the compound 40.
Example 12
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 48) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with a raw material A-48 and a raw material B-48 respectively to finally obtain an intermediate C-48;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-48, wherein the volume of a dichloromethane solution is 6 times that of the product C-48, and finally obtaining an intermediate D-48;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with an intermediate D-48 and a reactant E-48 respectively to finally obtain a compound 48.
Example 13
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 55) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with a raw material A-55 and a raw material B-55 respectively to finally obtain an intermediate C-55;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-55 to finally obtain an intermediate D-55;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with an intermediate D-55 and a reactant E-55 respectively to finally obtain a compound 55.
Example 14
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 60) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with a raw material A-60 and a raw material B-60 respectively to finally obtain an intermediate C-60;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-60 to finally obtain an intermediate D-60;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with an intermediate D-60 and a reactant E-60 respectively to finally obtain a compound 60.
Example 15
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 66) differs from the preparation of example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-66 and the raw material B-66 respectively to finally obtain an intermediate C-66;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-66 to finally obtain an intermediate D-66;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-66 and the reactant E-66 respectively to finally obtain the compound 66.
Example 16
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 71) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with a raw material A-71 and a raw material B-71 respectively to finally obtain an intermediate C-71;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-71 to finally obtain an intermediate D-71;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with an intermediate D-71 and a reactant E-71 respectively to finally obtain a compound 71.
Example 17
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 78) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-78 and the raw material B-78 respectively to finally obtain an intermediate C-78;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-78 to finally obtain an intermediate D-78;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-78 and the reactant E-78 respectively to finally obtain the compound 78.
Example 18
The preparation of an anthracene nitrogen-containing organic light-emitting compound (compound 82) differs from example 1 only in the following specific synthetic steps:
(1) replacing the raw material A-1 and the raw material B-1 in the step 1) with the raw material A-82 and the raw material B-82 respectively to finally obtain an intermediate C-82;
(2) replacing the intermediate C-1 in the step 2) with an intermediate C-82 to finally obtain an intermediate D-82;
(3) replacing the intermediate D-1 and the reactant E-1 in the step 3) with the intermediate D-82 and the reactant E-82 respectively to finally obtain the compound 82.
The mass spectra and the molecular formulae of the compounds obtained in examples 5 to 18 are shown in Table 1 below.
Table 1:
example 19
An organic electroluminescent device was prepared using compound 1 prepared in example 1, which is more specifically:
coating thickness of Fisher company of
The ITO glass substrate is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30min, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water, the ultrasonic cleaning is carried out for 10min, after the cleaning by distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and then are dried, the ITO glass substrate is transferred into a plasma cleaning machine, the substrate is cleaned for 5min, and the substrate is sent into an evaporation machine.
HAT-CN with a thickness of 10nm was vapor-deposited on the prepared ITO transparent electrode as a hole injection layer. N '-bis (1-naphthyl) -N, N' -diphenyl- (1, 1 '-biphenyl) -4, 4' -diamine (NPB) having a thickness of 80nm was vacuum-deposited on the formed hole injection layer as a hole transport layer. 4, 4'-N, N' -biphenyldicarbazole ("CBP") as a host material and a luminescent material doped with 5% FIrpic were then vapor-deposited on the above hole transport layer to a thickness of 20 nm. Then, bis (2-methyl-8-hydroxyquinoline-N1, 08) - (1, 1' -biphenyl-4-hydroxy) aluminum (BALq) as a hole-blocking layer was vacuum-evaporated on the above light-emitting layer to a thickness of 10 nm. A compound 1 having a thickness of 40nm was vacuum-deposited on the hole-blocking layer to form an electron-transporting layer. Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 1nm as an electron injection layer. Finally, aluminum with the thickness of 100nm is evaporated and plated as a cathode, so that the preparation of the organic electroluminescent device is completed.
And testing the performance luminescence characteristics of the obtained device. Thereby completing the fabrication of the organic electroluminescent device.
Example 20 example 36
An organic electroluminescent device differing from example 19 only in that:
corresponding organic electroluminescent devices were prepared by substituting compound 1 used in example 19 with compound 5, compound 8, compound 14, compound 18, compound 20, compound 29, compound 34, compound 40, compound 43, compound 48, compound 55, compound 60, compound 66, compound 71, compound 78, compound 82, and compound 83, respectively, as an electron transport layer.
Comparative example 1
An organic electroluminescent device differing from example 19 only in that:
the compound structure of the electron transport layer is as follows:
comparative example 2
An organic electroluminescent device differing from example 19 only in that:
the compound structure of the electron transport layer is as follows:
technical effects
The organic electroluminescent devices prepared in examples 19 to 36 and comparative examples 1 and 2 were applied with a forward direct current bias voltage, the organic electroluminescent characteristics were measured using a PR-650 photometric measuring instrument of Photo Research, and the lifetime of T95 was measured using a lifetime measuring apparatus of McScience at a reference gray level of 1000cd/m 2. The results are shown in Table 2.
Table 2:
compared with a comparative example, the driving voltage of the organic electroluminescent device provided by the invention is reduced by about 2V, the luminous efficiency is improved by about 12%, and the service life of the device is prolonged by about 50 h. From the results of the above table 2, it can be confirmed that the organic electroluminescent device prepared using the compound provided by the present invention as an electron transport material has high luminous efficiency and long life and reduced driving voltage.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. An anthracene nitrogen-containing organic light-emitting compound having the following structure:
2. the method according to claim 1, comprising the steps of:
1) dissolving a raw material A, a raw material B and sodium tert-butoxide in toluene under the protection of inert gas to obtain a mixture 1;
2) adding tris (dibenzylideneacetone) dipalladium and tris (tert-butyl) phosphorus into the mixture 1, and carrying out reflux stirring reaction for 12 hours at the temperature of 100 ℃ and 120 ℃ to obtain a mixture 2;
3) removing impurities from the mixture 2, washing, extracting, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, concentrating and purifying to obtain an intermediate product C;
4) adding NBS into a dichloromethane solution of an intermediate product C for reaction at room temperature, concentrating a reaction solution after the reaction is finished to obtain a concentrated solution, and dropwise adding the concentrated solution into stirred petroleum ether at room temperature to separate out a solid; after the solid is completely separated out, carrying out suction filtration and drying for 10-16h at 50-80 ℃ to obtain an intermediate product D;
5) adding the intermediate product D, the raw material E and potassium carbonate into a mixed solvent of toluene, ethanol and water, adding tetrakis (triphenylphosphine) palladium under the protection of inert gas, heating to 100-120 ℃, and reacting for 7-9h to obtain a compound shown in the general formula I;
the synthetic route of the general formula I is as follows:
3. the method according to claim 2, wherein the equivalent ratio of the raw material A, the raw material B and the sodium tert-butoxide in the step 1) is (0.8-1.2): (1.0-1.2): (2.8-3.2), and the volume ratio of the toluene to the raw material A is 1: (2-8).
4. The method for preparing the anthracene nitrogen-containing organic luminescent compound according to claim 2, wherein the impurity removal in the step 3) is performed by using diatomite; the washing is as follows: adding water for washing, wherein the extraction is to extract an organic phase by using dichloromethane; the concentration is reduced pressure concentration; the purification is to purify the concentrated product by column chromatography by using 300-400-mesh silica gel, and the eluent used in the purification process is a mixture of dichloromethane and petroleum ether with the volume ratio of 1 (5-7).
5. The method according to claim 2, wherein the volume ratio of the dichloromethane to the product C in the step 4) is 1: (3-6); the equivalent ratio of NBS to intermediate C is (1.0-1.2) to 1.0; the stirring speed was 300 and 1000 rpm.
6. The method according to claim 2, wherein the volume ratio of the toluene, ethanol and water in the step 5) is (2-4): (0.8-1.2): (0.8-1.2).
7. An organic electroluminescent device comprising: the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer, and the organic layer is characterized by further comprising an electron transport layer, and the electron transport layer is the anthracene nitrogen-containing organic light-emitting compound according to claim 1 or the anthracene nitrogen-containing organic light-emitting compound prepared by the preparation method according to any one of claims 2 to 6.
8. Use of an organic electroluminescent device as claimed in claim 7 in an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
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