CN116143780A - Spiro organic electroluminescent compounds containing hetero atom, preparation method and application thereof - Google Patents
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Abstract
The invention relates to a spiro organic electroluminescent compound containing hetero atoms, a preparation method and application thereof, belonging to the technical field of organic luminescent materials, wherein the spiro organic electroluminescent compound containing hetero atoms has a structural general formula of formula 1:
the invention provides a spiro organic electroluminescent compound containing hetero atoms, which has high electron injection and movement rate, good film forming property and thermal stability, and can remarkably improve the electron transmission rate from the electron transmission layer to the electron transmission layer of an organic electroluminescent deviceThe electron transmission efficiency of the light emitting layer is improved, so that the light emitting efficiency is improved, the driving voltage is reduced, and the service life of the device is prolonged.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a spiro organic electroluminescent compound containing hetero atoms, a preparation method and application thereof.
Background
Organic light emitting diodes (OLED: organic Light Emitting Diode) are increasingly coming into the field of view as a new and promising display technology. An OLED is an electroluminescent device formed from a multi-layer organic thin film structure.
The organic electroluminescent element is a self-luminous element utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: an anode, a cathode, and an organic material layer interposed therebetween. In order to improve efficiency and stability of the organic electroluminescent element, the organic material layer generally includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In such an organic light emitting element, when a voltage is applied between an anode and a cathode, holes from the anode and electrons from the cathode are injected into an organic material layer, and generated excitons generate light having a specific wavelength when they migrate to a ground state. The structure of the electron transport material used as the electron transport layer at present usually contains nitrogen-containing heterocycle such as pyridine, pyrimidine, oxadiazole, triazole, imidazole and the like with electron transport performance and electron-withdrawing groups such as phosphorus oxygen group, and as a key component in the OLED structure, the electron transport layer can also have great influence on the service life of the device, for example, the mobility and energy band structure of the material determine the local electric field, current carrier and joule heat distribution of the electron transport layer and the vicinity thereof, so that the aging speed of the organic material and the device is directly influenced.
The research of organic electroluminescent materials has been widely conducted in the academia and industry, but stable and efficient organic layer materials for organic electric elements have not been fully developed so far, and the industrialization process of the technology still faces a number of key problems, so the development of new materials is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a spiro organic electroluminescent compound containing hetero atoms, a preparation method and application thereof, so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a spiro organic electroluminescent compound containing hetero atoms has a structural general formula of formula 1:
wherein n is 0, 1, 2 or 3, m is 0, 1, 2, 3 or 4, n and m are not 0 at the same time;
L 1 、L 2 are identical to or different from each other, and are each independently a link key; substituted or unsubstituted C 6 -C 30 Arylene of (a); substituted or unsubstituted C 3 -C 30 Heteroarylene;
R 1 、R 2 、R 3 0-4 substituents, R 1 -R 3 Identical or different from each other, R 1 -R 3 Each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silicon-based, borane-based; substituted or unsubstituted C 1 -C 30 An alkyl group; substituted or unsubstituted C 2 -C 30 Alkenyl groups; substituted or unsubstituted C 2 -C 30 Alkynyl; substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 20-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 25-membered heteroarylamine group having a heteroatom selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C 6 -C 60 An arylamine group;
Ar 1 、Ar 2 identical or different from each other, ar 1 、Ar 2 Each independently is a substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 20-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 30-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 30-membered heteroaryl amine group, the heteroatom of which is selected from oxygen, nitrogen or sulfur.
As a further technical scheme of the invention, n and m are respectively 0 or 1 independently, and n and m are not 0 at the same time.
As a further technical scheme of the invention, n and m are 1 at the same time.
As a still further aspect of the present invention, the L 1 、L 2 Are identical to or different from each other, and are each independently a link key; substituted or unsubstituted C 6 -C 18 Arylene of (a); substituted or unsubstituted C 3 -C 15 Heteroarylene;
the R is 1 -R 3 Are the same or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino; substituted or unsubstituted C 1 -C 15 An alkyl group; substituted or unsubstituted C 3 -C 10 Cycloalkyl; a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 20 An aryl group; a substituted or unsubstituted 3-to 10-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur;
the Ar is as follows 1 、Ar 2 Are each, identically or differently, oxazole, oxadiazole, triazole, triazene, imidazole, thiazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, benzothiadiazole, quinoline, quinoxaline, cinnoline, naphthyridine, anthracene, diazoanthracene, naphthacene, dibenzofuran, dibenzothiophene, benzodifuran, benzodithiophene, benzodioxazole, benzodithiazole.
As the inventionIn still a further aspect, the L 1 、L 2 Identical or different from each other, said L 1 、L 2 Each independently is a linking bond, substituted or unsubstituted C 6 -C 18 Arylene of (C) substituted or unsubstituted 3 -C 10 Heteroarylene;
the R is 1 -R 3 Are the same or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino; substituted or unsubstituted C 1 -C 10 An alkyl group; substituted or unsubstituted C 3 -C 10 Cycloalkyl; a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 18 An aryl group; a substituted or unsubstituted 3-to 10-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur;
the Ar is as follows 1 、Ar 2 Are identical or different from one another and are each independently of one another oxazoles, oxadiazoles, triazoles, imidazoles, thiazoles, pyridines, pyrimidines, triazines, quinolines, quinoxalines, diazoxanes.
As a still further aspect of the present invention, the general formula 1 is one of the following formulas 1-1 to 1-9:
wherein L in the formulae 1-1 to 1-9 1 、L 2 、Ar 1 、Ar 2 、R 1 -R 3 As defined in equation 1 above.
As a still further technical scheme of the invention, the spiro organic electroluminescent compound containing hetero atoms is one of the following structural formulas 1-248:
a preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following steps:
preparation of intermediate 1: dissolving the raw material 2 in THF, slowly adding n-BuLi after ventilation and cooling, adding the raw material 1 under the protection of nitrogen after reaction, slowly heating and stirring to prepare an intermediate 1;
preparation of intermediate 2: adding the intermediate 1 into a reaction bottle, adding glacial acetic acid, heating, and then dropwise adding concentrated sulfuric acid to prepare an intermediate 2;
preparing a spiro organic electroluminescent compound containing hetero atoms: adding the intermediate 2 and the raw material 3 and/or the raw material 4 into a mixed solution of toluene, ethanol and water, adding a palladium catalyst and potassium carbonate under the protection of nitrogen after ventilation, uniformly stirring, and heating for reaction to prepare a spiro organic electroluminescent compound containing hetero atoms;
the synthetic route is as follows:
wherein L is 1 、L 2 、Ar 1 、Ar 2 、R 1 -R 3 As defined in equation 1 above.
Preferably, the preparation intermediate 1 is: dissolving the raw material 2 in THF, then ventilating for 3 times, cooling to-78 ℃, slowly adding n-BuLi, reacting for 2 hours, adding the raw material 1 under the protection of nitrogen, slowly heating to 25 ℃, stirring for 10 hours, then slowly adding distilled water into the reaction solution to quench the reaction, and extracting the reaction solution with DCM; the extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator; precipitation of solid with DCM and PE (volume ratio 1:4) to afford intermediate 1;
the preparation intermediate 2 is as follows: adding the intermediate 1 into a reaction bottle, adding glacial acetic acid with the volume of 10 times to raise the temperature to 80 ℃, slowly dripping concentrated sulfuric acid with the volume of 1 time, after the dripping is finished, adding distilled water with the volume of 20 times of concentrated sulfuric acid, and completely precipitating, filtering and drying solids to obtain an intermediate 2;
the preparation of the spiro organic electroluminescent compound containing hetero atoms comprises the following steps: adding the intermediate 2 and the raw materials 3 and/or 4 into a mixed solution of toluene, ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; purifying the remaining material by column chromatography to obtain spiro organic electroluminescent compounds containing hetero atoms as shown in chemical formula 1.
An electron transport layer comprising a spiro-ring organic electroluminescent compound containing a heteroatom as described above.
An organic electroluminescent device comprising an electron transport layer as described above.
Compared with the prior art, the invention has the beneficial effects that: the spiro organic electroluminescent compound containing the hetero atoms has high electron injection and movement rate, good film forming property and thermal stability, and can obviously improve the electron transmission efficiency from the electron transmission layer to the light-emitting layer when being used in the electron transmission layer of an organic electroluminescent device, thereby improving the light-emitting efficiency, reducing the driving voltage and prolonging the service life of the device.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a spiro-type organic electroluminescent compound containing a heteroatom prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a spiro-type organic electroluminescent compound containing hetero atoms prepared in example 2;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of a spiro-type organic electroluminescent compound containing hetero atoms prepared in example 3.
Detailed Description
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
preparation of intermediate 1: dissolving the raw material 2 in THF, slowly adding n-BuLi after ventilation and cooling, adding the raw material 1 under the protection of nitrogen after reaction, slowly heating and stirring to prepare an intermediate 1;
preparation of intermediate 2: adding the intermediate 1 into a reaction bottle, adding glacial acetic acid, heating, and then dropwise adding concentrated sulfuric acid to prepare an intermediate 2;
preparing a spiro organic electroluminescent compound containing hetero atoms: adding the intermediate 2 and the raw material 3 into a mixed solution of toluene, ethanol and water, adding a palladium catalyst and potassium carbonate under the protection of nitrogen after ventilation, stirring uniformly, and heating for reaction to prepare the spiro organic electroluminescent compound containing hetero atoms.
In the above synthetic route, n is 0, 1, 2 or 3, m is 0, 1, 2, 3 or 4, n and m are not 0 at the same time;
L 1 、L 2 are identical to or different from each other, and are each independently a link key; substituted or unsubstituted C 6 -C 30 Arylene of (a); substituted or unsubstituted C 3 -C 30 Heteroarylene;
R 1 、R 2 、R 3 0-4 substituents, R 1 -R 3 Identical or different from each other, R 1 -R 3 Each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silicon-based, borane-based; substituted or unsubstituted C 1 -C 30 An alkyl group; substituted or unsubstituted C 2 -C 30 Alkenyl groups; substituted or unsubstituted C 2 -C 30 Alkynyl; substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 20-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 25-membered heteroarylamine group having a heteroatom selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C 6 -C 60 An arylamine group;
Ar 1 、Ar 2 identical or different from each other, ar 1 、Ar 2 Each independently is a substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 20-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 30-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 30-membered heteroaryl amine group, the heteroatom of which is selected from oxygen, nitrogen or sulfur.
The spiro organic electroluminescent compounds containing hetero atoms prepared by the preparation method are selected from one of the following chemical formulas 1-248:
example 1
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
raw material 2 (44.6 mmol) and 100ml THF are added into a reaction vessel, ventilation is carried out for 3 times, the temperature is reduced to minus 78 ℃, 2.5mol/L n-BuLi (17.8 ml,44.6 mmol) is added under the nitrogen atmosphere and stirred for 2 hours, raw material 1 (37 mmol) is added, the temperature is increased to 25 ℃, and the stirring is carried out for 10 hours, thus completing the reaction; distilled water was then added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and the solid was precipitated with DCM and PE (volume ratio 1:4) to give intermediate 1 (13.99 g, 75.3% yield).
Intermediate 1 (27.84 mmol) was added to a reaction flask, 240ml of glacial acetic acid was added, the temperature was raised to 80 ℃, 12ml of concentrated sulfuric acid was added dropwise, the reaction was completed after the dropwise addition, then 240ml of distilled water was added, and the solid was precipitated and dried to obtain intermediate 2 (10.31 g, yield 76.5%).
Adding the intermediate 2 (15 mmol) and the raw material 3 (15 mmol) into a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to obtain compound 2 (5.84 g, yield 61.2%, MW: 636.76).
The resulting compound 2 was subjected to detection analysis, and the results were as follows:
HPLC purity: > 99.5%;
mass spectrometry test: theoretical value 636.76; the test value was 636.35;
elemental analysis:
the calculated values are: c,86.77; h,4.43; n,8.80;
the test values are: c,85.86; h,4.71; n,8.98.
Example 2
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
raw material 2 (44.6 mmol) and 100ml THF are added into a reaction vessel, ventilation is carried out for 3 times, the temperature is reduced to minus 78 ℃, 2.5mol/L n-BuLi (17.8 ml,44.6 mmol) is added under the nitrogen atmosphere and stirred for 2 hours, raw material 1 (37 mmol) is added, the temperature is increased to 25 ℃, and the stirring is carried out for 10 hours, thus completing the reaction; distilled water was then added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and the solid was precipitated with DCM and PE (volume ratio 1:4) to give intermediate 1 (14.13 g, 76.1% yield).
Intermediate 1 (28.12 mmol) was added to a reaction flask, 240ml of glacial acetic acid was added, the temperature was raised to 80 ℃, 12ml of concentrated sulfuric acid was added dropwise, the reaction was completed after the dropwise addition, then 240ml of distilled water was added, and the solid was precipitated and dried to obtain intermediate 2 (10.27, yield 75.41%).
Adding the intermediate 2 (15 mmol) and the raw material 3 (15 mmol) into a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to give compound 26 (6.69 g, yield 62.6%, MW: 712.86).
The resulting compound 26 was subjected to detection analysis, and the result was as follows:
HPLC purity: > 99.5%;
mass spectrometry test: theoretical value 712.86; the test value was 712.53;
elemental analysis:
the calculated values are: c,87.62; h,4.52; n,7.86;
the test values are: c,87.03; h,4.81; n,7.99.
Example 3
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
raw material 2 (44.6 mmol) and 100ml THF are added into a reaction vessel, ventilation is carried out for 3 times, the temperature is reduced to minus 78 ℃, 2.5mol/L n-BuLi (17.8 ml,44.6 mmol) is added under the nitrogen atmosphere and stirred for 2 hours, raw material 1 (37 mmol) is added, the temperature is increased to 25 ℃, and the stirring is carried out for 10 hours, thus completing the reaction; distilled water was then added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and the solid was precipitated with DCM and PE (volume ratio 1:4) to give intermediate 1 (14.06 g, 75.69% yield).
Intermediate 1 (27.98 mmol) was added to a reaction flask, 240ml of glacial acetic acid was added, the temperature was raised to 80 ℃, 12ml of concentrated sulfuric acid was added dropwise, the reaction was completed after the dropwise addition was completed, then 240ml of distilled water was added, and the solid was precipitated and dried to obtain intermediate 2 (10.07 g, yield 74.38%).
Adding the intermediate 2 (15 mmol) and the raw material 3 (15 mmol) into a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to give compound 66 (6.25 g, yield 62.1%, MW: 711.87).
The resulting compound 66 was subjected to detection analysis, and the results were as follows:
HPLC purity: > 99.5%.
Mass spectrometry test: theoretical value 711.87; the test value was 711.53;
elemental analysis:
the calculated values are: c,89.42; h,4.67; n,8.80;
the test values are: c,85.86; h,4.71; n,8.98.
Example 4
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
raw material 2 (44.6 mmol) and 100ml THF are added into a reaction vessel, ventilation is carried out for 3 times, the temperature is reduced to minus 78 ℃, 2.5mol/L n-BuLi (17.8 ml,44.6 mmol) is added under the nitrogen atmosphere and stirred for 2 hours, raw material 1 (37 mmol) is added, the temperature is increased to 25 ℃, and the stirring is carried out for 10 hours, thus completing the reaction; distilled water was then added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and the solid was precipitated with DCM and PE (volume ratio 1:4) to give intermediate 1 (14.0 g, 75.4% yield).
Intermediate 1 (27.86 mmol) was added to a reaction flask, 240ml of glacial acetic acid was added, the temperature was raised to 80 ℃, 12ml of concentrated sulfuric acid was added dropwise, the reaction was completed after the dropwise addition, then 240ml of distilled water was added, and the solid was precipitated and dried to obtain intermediate 2 (10.06 g, yield 74.58%).
Adding the intermediate 2 (15 mmol) and the raw material 3 (15 mmol) into a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to give compound 158 (7.01 g, yield 62.14%, MW: 752.92).
The resulting compound 158 was analyzed and the results were as follows:
HPLC purity: > 99.4%;
mass spectrometry test: theoretical value 752.92; the test value was 753.24;
elemental analysis:
the calculated values are: c,87.74; h,4.82; n,7.44;
the test values are: c,87.61; h,4.96; n,7.67.
Example 5
A preparation method of spiro organic electroluminescent compounds containing hetero atoms comprises the following synthetic routes:
the preparation method specifically comprises the following steps:
raw material 2 (44.6 mmol) and 100ml THF are added into a reaction vessel, ventilation is carried out for 3 times, the temperature is reduced to minus 78 ℃, 2.5mol/L n-BuLi (17.8 ml,44.6 mmol) is added under the nitrogen atmosphere and stirred for 2 hours, raw material 1 (37 mmol) is added, the temperature is increased to 25 ℃, and the stirring is carried out for 10 hours, thus completing the reaction; distilled water was then added to the reaction solution to quench the reaction, and the reaction solution was extracted with DCM; the extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and the solid was precipitated with DCM and PE (volume ratio 1:4) to give intermediate 1 (13.97 g, 75.24% yield).
Intermediate 1 (27.80 mmol) was added to a reaction flask, 240ml of glacial acetic acid was added, the temperature was raised to 80 ℃, 12ml of concentrated sulfuric acid was added dropwise, the reaction was completed after the dropwise addition was completed, then 240ml of distilled water was added, and the solid was precipitated and dried to obtain intermediate 2 (10.63 g, yield 76.2%).
Adding the intermediate 2 (15 mmol) and the raw material 3 (15 mmol) into a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding a palladium catalyst and potassium carbonate under the protection of nitrogen, uniformly stirring, heating to 95 ℃, reacting for 10 hours, and then extracting the mixture with dichloromethane and water; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to give compound 178 (7.23 g, yield 61.3%, MW: 787.97).
The resulting compound 178 was analyzed and the results were as follows:
HPLC purity: > 99.6%;
mass spectrometry test: theoretical value 787.97; the test value was 787.73;
elemental analysis:
the calculated values are: c,89.93; h,4.73; n,5.33;
the test values are: c,89.68; h,4.89; n,5.46.
The synthesis methods of other compounds are the same as those of the above examples, and are not described in detail herein, and mass spectra, molecular formulas and yields of other synthesis examples are shown in table 1 below:
TABLE 1
Application example 1
A preparation method of an organic electroluminescent device comprises the following steps:
a. ITO anode: washing an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing by ultrasonic waves for 30min, repeatedly washing by distilled water for 2 times, washing by ultrasonic waves for 10min, transferring into a spin dryer for spin drying after washing, baking for 2 hours at 220 ℃ by a vacuum oven, and cooling after baking is finished, so that the glass substrate can be used; using the substrate as an anode, and using an evaporator to perform an evaporation device process, and evaporating other functional layers on the substrate in sequence;
b. HIL (hole injection layer): to be used for
Vacuum vapor plating the hole injection layer materials HT-1 and P-dopant, the chemical formulas of which are shown as follows; the evaporation rate ratio of HT-1 to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): to be used for
Vacuum evaporating 130nm HT-1 on the hole injection layer as hole transport layer, and the structure is shown in the figure;
d. EBL (electron blocking layer): to be used for
Vacuum evaporating 10nm on the hole transmission layer to serve as an EBL-1 electron blocking layer;
e. EML (light emitting layer): then on the electron blocking layer to
A Host material (Host) and a Dopant material (Dopant) having a thickness of 20nm were vacuum-deposited as light-emitting layers, the chemical formulas of Host and Dopant being as follows; wherein the evaporation rate ratio of Host to Dopant is 98:2;
f. HBL (hole blocking layer): to be used for
Is at a vapor deposition rate of light emissionVacuum evaporation is carried out on the HB-1 with the thickness of 5nm on the layer to serve as a hole blocking layer, and the structure is shown in the figure;
g. ETL (electron transport layer): to be used for
Vapor-depositing 30nm of the compound 2 provided in the above example as an electron transport layer on top of the hole blocking layer in vacuo;
h. EIL (electron injection layer): to be used for
Evaporating Yb film layer with a thickness of 1.0nm to form an electron injection layer;
i. and (3) cathode: to be used for
Vapor deposition rate ratio of magnesium and silver is 18nm, and the vapor deposition rate ratio is 1:9, so that an OLED device is obtained;
j. light extraction layer: to be used for
CPL-1 with the thickness of 70nm is vacuum evaporated on the cathode to be used as a light extraction layer; packaging the evaporated substrate; firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The structural formula of the materials used in the preparation method is shown as follows:
application examples 2 to 50
Application examples 2-50 referring to the method of application example 1 described above, the corresponding organic electroluminescent device was prepared by replacing compound 2 used in device example 1 with compounds 3, 21, 23, 26, 28, 31, 34, 39, 41, 65, 66, 68, 82, 84, 95, 111, 112, 122, 127, 131, 135, 139, 143, 146, 158, 160, 162, 164, 166, 168, 169, 172, 175, 177, 178, 181, 183, 185, 188, 190, 191, 192, 198, 200, 201, 202, 204, 216, 220 as electron transport layers, respectively.
Comparative examples 1 to 2
The only difference between the preparation method of the organic electroluminescent device and the application example 1 is that the organic electroluminescent device adopts the existing comparison compound a and the compound b to replace the electron transport layer (compound 2) in the application example 1 for evaporation, so as to prepare the comparison examples 1-2; wherein, the chemical structural formulas of the comparison compounds a and b are respectively as follows:
the organic electroluminescent devices obtained in the above application examples 1 to 50 and comparative examples 1 to 2 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 test results (brightness value 1000 cd/m) 2 )
As can be seen from table 2: compared with the organic electroluminescent devices prepared by taking the compound a and the compound b as the electron transport layers, the organic electroluminescent devices prepared by taking the spiro organic electroluminescent compounds containing the hetero atoms as the electron transport layers have lower starting voltage, and the luminous efficiency and the service life are obviously improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The spiro organic electroluminescent compound containing hetero atoms is characterized in that the spiro organic electroluminescent compound containing hetero atoms has a structural general formula of formula 1:
wherein n is 0, 1, 2 or 3, m is 0, 1, 2, 3 or 4, n and m are not 0 at the same time;
L 1 、L 2 are identical to or different from each other, and are each independently a link key; substituted or unsubstituted C 6 -C 30 Arylene of (a); substituted or unsubstituted C 3 -C 30 Heteroarylene;
R 1 、R 2 、R 3 0-4 substituents, R 1 -R 3 Identical or different from each other, R 1 -R 3 Each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silicon-based, borane-based; substituted or unsubstituted C 1 -C 30 An alkyl group; substituted or unsubstituted C 2 -C 30 Alkenyl groups; substituted or unsubstituted C 2 -C 30 Alkynyl; substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 20-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 25-membered heteroarylamine group having a heteroatom selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C 6 -C 60 An arylamine group;
Ar 1 、Ar 2 identical or different from each other, ar 1 、Ar 2 Each independently is a substituted or unsubstituted C 3 -C 30 Cycloalkyl; a substituted or unsubstituted 3-to 20-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 30 An aryl group; a substituted or unsubstituted 3-to 30-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur; a substituted or unsubstituted 3-to 30-membered heteroaryl amine group, the heteroatom of which is selected from oxygen, nitrogen or sulfur.
2. The spiro-ring organic electroluminescent compound according to claim 1, wherein n and m are each independently 0 or 1, and n and m are not 0 at the same time.
3. The spiro-ring organic electroluminescent compound according to claim 2, wherein n and m are 1 at the same time.
4. The spiro-compound containing a heteroatom according to claim 1, wherein L 1 、L 2 Each otherThe same or different, each independently a link key; substituted or unsubstituted C 6 -C 18 Arylene of (a); substituted or unsubstituted C 3 -C 15 Heteroarylene;
the R is 1 -R 3 Are the same or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino; substituted or unsubstituted C 1 -C 15 An alkyl group; substituted or unsubstituted C 3 -C 10 Cycloalkyl; a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 20 An aryl group; a substituted or unsubstituted 3-to 10-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur;
the Ar is as follows 1 、Ar 2 Are each, identically or differently, oxazole, oxadiazole, triazole, triazene, imidazole, thiazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, benzothiadiazole, quinoline, quinoxaline, cinnoline, naphthyridine, anthracene, diazoanthracene, naphthacene, dibenzofuran, dibenzothiophene, benzodifuran, benzodithiophene, benzodioxazole, benzodithiazole.
5. The spiro organic electroluminescent compound as claimed in claim 4, wherein L is 1 、L 2 Identical or different from each other, said L 1 、L 2 Each independently is a linking bond, substituted or unsubstituted C 6 -C 18 Arylene of (C) substituted or unsubstituted 3 -C 10 Heteroarylene;
the R is 1 -R 3 Are the same or different from each other and are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino; substituted or unsubstituted C 1 -C 10 An alkyl group; substituted or unsubstituted C 3 -C 10 Cycloalkyl; a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, the heteroatom of which is selected from oxygen, nitrogen or sulfur; substituted or unsubstituted C 6 -C 18 An aryl group; a substituted or unsubstituted 3-to 10-membered heteroaryl group having a heteroatom selected from oxygen, nitrogen or sulfur;
the Ar is as follows 1 、Ar 2 Are identical or different from one another and are each independently of one another oxazoles, oxadiazoles, triazoles, imidazoles, thiazoles, pyridines, pyrimidines, triazines, quinolines, quinoxalines, diazoxanes.
6. The heteroatom containing spiro organic electroluminescent compound according to claim 1, wherein the general formula 1 is one of the following formulas 1-1 to 1-9:
wherein L in the formulae 1-1 to 1-9 1 、L 2 、Ar 1 、Ar 2 、R 1 -R 3 As defined in equation 1 above.
7. The heteroatom containing spiro organic electroluminescent compound of claim 1, wherein the heteroatom containing spiro organic electroluminescent compound is one of the following structural formulas 1-248:
8. a process for the preparation of a spiro organic electroluminescent compound containing heteroatoms as claimed in any one of claims 1 to 7, comprising the steps of:
preparation of intermediate 1: dissolving the raw material 2 in THF, slowly adding n-BuLi after ventilation and cooling, adding the raw material 1 under the protection of nitrogen after reaction, slowly heating and stirring to prepare an intermediate 1;
preparation of intermediate 2: adding the intermediate 1 into a reaction bottle, adding glacial acetic acid, heating, and then dropwise adding concentrated sulfuric acid to prepare an intermediate 2;
preparing a spiro organic electroluminescent compound containing hetero atoms: adding the intermediate 2 and the raw material 3 into a mixed solution of toluene, ethanol and water, adding a palladium catalyst and potassium carbonate under the protection of nitrogen after ventilation, stirring uniformly, and heating for reaction to prepare a spiro organic electroluminescent compound containing hetero atoms;
wherein, the structural formulas of the raw material 1, the raw material 2, the intermediate 1 and the intermediate 2 are as follows:
the raw material 3 is
And/or +.>
/>
Wherein the L is 1 、L 2 、Ar 1 、Ar 2 、R 1 -R 3 As defined in equation 1 above.
9. An electron transport layer comprising the heteroatom-containing spiro-type organic electroluminescent compound according to any one of claims 1 to 7.
10. An organic electroluminescent device comprising the electron transport layer according to claim 9.
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