CN115925661B - Light-emitting auxiliary material, preparation method and application thereof in organic electroluminescent device - Google Patents
Light-emitting auxiliary material, preparation method and application thereof in organic electroluminescent device Download PDFInfo
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- CN115925661B CN115925661B CN202211697287.9A CN202211697287A CN115925661B CN 115925661 B CN115925661 B CN 115925661B CN 202211697287 A CN202211697287 A CN 202211697287A CN 115925661 B CN115925661 B CN 115925661B
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 10
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
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- 230000005540 biological transmission Effects 0.000 abstract description 7
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
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Abstract
The invention belongs to the technical field of organic luminescent materials, relates to an organic compound and a preparation method thereof, and an organic electroluminescent device, and in particular relates to a luminescent auxiliary material and a preparation method thereof, and application of the luminescent auxiliary material in the organic electroluminescent device. The luminescent auxiliary material disclosed by the invention has a structure shown in a general formula I in the specification. The aromatic amine group has strong hole transmission capability, the triarylamine structure can reduce the crystallinity of molecules, reduce the planeness of the molecules, prevent the molecules from moving on the plane, and simultaneously reduce the driving voltage of the device and improve the efficiency of the organic electroluminescent device due to high hole transmission rate.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and relates to a luminescent auxiliary material, a preparation method thereof and application thereof in preparation of an organic electroluminescent device.
Background
OLED materials are classified into light emitting materials, hole materials, electron materials, etc. Among them, the hole transport material generally has a low Highest Occupied Molecular Orbital (HOMO) value, excitons generated in the light emitting layer diffuse to the hole transport layer interface or hole transport layer side, eventually causing light emission at the light emitting layer interface or charge imbalance in the light emitting layer, thereby emitting light at the interface of the hole transport layer, making the color purity and efficiency of the organic electroluminescent device low, and the lifetime short.
The light-emitting auxiliary layer is introduced between the light-emitting layer and the hole transport layer, so that the technical problems can be effectively avoided.
At present, materials used as a light-emitting auxiliary layer are limited, most of the materials adopt fluorene ring structures, the fluorene ring structures have higher hole mobility, meanwhile, the excitons after blocking recombination by higher T1 energy are outwards spread to a transmission layer, the overall efficiency of the device is improved, and meanwhile, the transmission potential barrier of holes from the transmission layer to the light-emitting layer is reduced by a proper HOMO value, so that the driving voltage of the device is reduced and the service life of the device is prolonged.
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 sufficiently developed so far, and the industrialization progress of the technology still faces a number of key problems. Therefore, how to develop a new luminescent auxiliary material is always a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a luminescent auxiliary material, a preparation method thereof and application thereof in an organic electroluminescent device.
In order to achieve the above object, a first object of the present invention is to provide a light-emitting auxiliary material.
The technical scheme is as follows:
a luminescent auxiliary material having a structure represented by general formula I:
wherein,
x is O or S;
ar is independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 20-membered heteroaryl, wherein the heteroatoms are selected from oxygen, nitrogen, sulfur; ar is fused with any position on the benzene ring;
the chemical structural formula of L is shown as formula I, and L cannot be a connecting bond:
in the formula I, R 2 Selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, wherein the heteroatoms are selected from the group consisting of oxygen, nitrogen, and sulfur; a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
R 1 selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur; a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
Ar 1 ,Ar 2 are identical or different from each other and are each independently selected from substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatoms of which are selected from oxygen, nitrogen and sulfur; a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur.
Further, ar is phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl; ar is condensed with adjacent benzene rings on the parent nucleus and is combined into a ring; the position where Ar may be condensed with the benzene ring may be 1,2 or 2,3 or 3, 4.
Namely, the molecular formula of the organic compound is shown as the general formulas (II-1) - (II-9):
further, it is preferable that L is the following group:
R 1 further preferred is:
further preferably Ar 1 ,Ar 2 Is a group obtained by arbitrarily combining the following groups:
wherein, in the above formula, the expression is the connection point
In this specification, "substituted" means substituted with one, two or more substituents selected from: C1-C20 alkyl, C1-C20 alkoxy, C6-C30 aryl, C6-C30 heteroaryl, wherein the heteroatoms are selected from oxygen, nitrogen, sulfur.
The aryl groups in the present specification are each independently selected from any one of phenyl, naphthyl, anthryl, phenanthryl, naphthaceneyl, pyrenyl, perylenyl, indenyl, acenaphthylenyl, triphenylenyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, benzodiphenylfluorenyl, phenylfluorenyl, spirofluorenyl, benzospirofluorenyl, biphenyl, p-terphenyl, and m-terphenyl.
Heteroaryl groups described in this specification are each independently selected from thienyl, furyl, pyrrolyl, benzothienyl, benzofuryl, indolyl, dibenzofuryl, dibenzothienyl, pyrazolyl, benzopyrazolyl, benzimidazolyl, imidazolyl, carbazolyl, benzonaphthofuryl, benzonaphthothienyl, benzocarbazolyl, dinaphthofuryl, dinaphthiothienyl, pyridyl, naphthyridinyl, acridinyl, pyridazinyl, phenothiazinyl, benzoxazinyl, pyridyl, bipyridyl, pyrimidinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl any one of pyrazinyl, triazinyl, diazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, benzothiadiazolyl, pyrimidinyl, pyrazinyl, benzimidazolyl, indolyl, quinolinyl, pyridazinyl, phthalazinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenanthroline, naphthyridinyl, benzoxazinyl, benzothiazinyl, azacarbazolyl, azadimethylfluorenyl, azadiphenylfluorenyl, azabenzodimethylfluorenyl, azabenzodiphenylfluorenyl, azaspirofluorenyl, azabenzospirofluorenyl.
In this specification, the alkyl group may be straight-chain or branched, and is independently selected from any one of methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethylpropyl, 1-dimethylpropyl, adamantyl, isohexyl, 4-methylhexyl.
In the present specification, the cycloalkyl groups may be each independently selected from any one of 5-methylhexylcyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl or cyclooctyl.
In the present specification, the alkoxy groups may be each independently selected from any one of methoxy, ethoxy, propoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, and hexyloxy.
Further, the above compound is selected from any one of the compounds represented by the following structural formulas:
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another object of the present invention is to provide a method for preparing the above luminescent auxiliary material, wherein the synthetic route of formula I is:
in the above formula, R 1 、X、L、Ar、Ar 1 And Ar is a group 2 Identical to the above-mentioned representation of the formula I, hal 1 、Hal 2 And Hal 3 Each independently selected from fluorine, chlorine, bromine or iodine.
The preparation method specifically comprises the following steps:
(1) After dissolving raw material A and raw material B in toluene, in N 2 Pd addition under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-Buona, heating to 110-120 ℃ and stirring for reaction for 8-12h, filtering with diatomite while the reaction is hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid, retaining an organic phase, extracting an aqueous phase with ethyl acetate, drying the combined organic layer with magnesium sulfate, removing a solvent with a rotary evaporator, and finally purifying the rest substances with column chromatography with a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound shown as the intermediate 1.
(2) Intermediate 1 and starting material C were dissolved in toluene at N 2 Pd addition under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-Buona, heating to 110-120 ℃ and stirring for reaction for 8-12h, filtering with diatomite while the reaction is hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid to keep an organic phase, extracting the aqueous phase with ethyl acetate, drying the combined organic layer with magnesium sulfate, removing solvent with a rotary evaporator, and finally purifying the residual substances with column chromatography with a mixture of dichloromethane and petroleum ether as eluent to obtain the compound shown as the intermediate 2.
Note that: in the reaction step, two halogens exist in the raw material C, the preparation of the intermediate with the target structure is realized by utilizing the characteristic that the reactivity I is larger than Br > Cl in the Buchwald-Hartwig coupling reaction, and the target compound is obtained by purifying the reaction by using a column chromatography or a silica gel funnel to remove byproducts.
The reaction mechanism is as follows:
transition metal organic chemistry (original sixth edition), robert H-crabtree (Robert H.Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
(3) At N 2 Under the protection, respectively adding the intermediate 2, the raw material D, the tetra (triphenylphosphine) palladium and the potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 90-100 ℃ for reaction for 8-10 hours, cooling to room temperature after the reaction is finished, washing with water to remove salt after the solid is separated out, leaching with a small amount of ethanol, drying a filter cake, and purifying the residual substances by using a column chromatography with a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound shown in the general formula 1.
A third object of the present invention is to provide an application of a light-emitting auxiliary material in an organic electroluminescent device.
Compared with the prior art, the invention relates to a luminescent auxiliary material, a preparation method and application thereof in an organic electroluminescent device. The aromatic amine group in the structure has strong hole transmission capability, the triarylamine structure can reduce the crystallinity of molecules, reduce the planeness of the molecules, prevent the molecules from moving on the plane, and simultaneously, the high hole transmission rate can reduce the driving voltage of the device and improve the efficiency of the organic electroluminescent device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate 2 in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound P-1 of example 1.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the accompanying drawings, wherein it is apparent that the embodiments described are only some, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
Example 1: synthesis of Compound P-1
The preparation method comprises the following specific steps:
1) After dissolving raw material A (1.0 eq) and raw material B (1.0 eq) in toluene, in N 2 Pd addition under atmosphere 2 (dba) 3 (0.02eq)、P(t-Bu) 3 (0.05 eq) and t-BuONa (2.0 eq), heating to 120 ℃ and stirring for reaction for 12h, filtering with diatomaceous earth while hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating the liquid to keep an organic phase, extracting the aqueous phase with ethyl acetate, then drying the combined organic layer with magnesium sulfate, removing the solvent with a rotary evaporator, and finally purifying the remaining material with column chromatography with a mixture of dichloromethane and petroleum ether (V: v=1:20) as eluent to obtain the compound shown as intermediate 1 (yield: 74.38%);
2) Intermediate 1 (1.0 eq) and starting material C (1.0 eq) were dissolved in toluene and then reacted in N 2 Pd addition under atmosphere 2 (dba) 3 (0.02eq)、P(t-Bu) 3 (0.05 eq) and t-Buona (2.0 eq), heating to 120 ℃ and stirring for reaction for 8h, filtering with diatomite while hot after the reaction, removing salt and catalystAfter cooling the filtrate to room temperature, distilled water was added to the filtrate to wash, an organic phase was retained after separation, the aqueous phase was extracted with ethyl acetate, the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: v=1:14) as an eluent to give the compound represented by intermediate 2 (yield: 68.65%).
3) At N 2 Under protection, respectively adding an intermediate 2 (1.0 eq), a raw material D (1.1 eq), tetrakis (triphenylphosphine) palladium (0.01 eq) and potassium carbonate (2.0 eq) into a mixed solvent of toluene, ethanol and water, heating to 100 ℃ for reaction for 10 hours, cooling to room temperature after the reaction is finished, after the solid is separated out, washing with water to remove salt after suction filtration, eluting with a small amount of ethanol, drying a filter cake, and purifying the residual substance by using a column chromatography with a mixture of dichloromethane and petroleum ether (V: V=1:10) as an eluent to obtain a compound P-1; (yield: 62.85%).
The compound P-1 obtained was analyzed and the results were as follows:
mass spectrometry test: theoretical value 689.86; the test value was 690.08.
Elemental analysis:
the calculated values are: c,90.54; h,5.11; n,2.03; o,2.32.
The test values are: c,90.25; h,5.28; n,2.19; o,2.43.
Example 2: synthesis of Compound P-20
1) After dissolving raw material A (1.0 eq) and raw material B (1.0 eq) in toluene, in N 2 Pd addition under atmosphere 2 (dba) 3 (0.02eq)、P(t-Bu) 3 (0.05 eq) and t-Buona (2.0 eq), heating to 120 ℃ and stirring for reaction for 12h, filtering with diatomaceous earth while hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating the liquid to retain an organic phase, extracting the aqueous phase with ethyl acetate, thenThe combined organic layers were dried over magnesium sulfate and the solvent was removed using a rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: v=1:20) as eluent to give the compound shown as intermediate 1 (yield: 74.25%);
2) Intermediate 1 (1.0 eq) and starting material C (1.0 eq) were dissolved in toluene and then reacted in N 2 Pd addition under atmosphere 2 (dba) 3 (0.02eq)、P(t-Bu) 3 (0.05 eq) and t-BuONa (2.0 eq), heating to 120 ℃ and stirring for reaction for 8 hours, filtering with diatomite while the reaction is hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid to keep an organic phase, extracting the aqueous phase with ethyl acetate, then drying the combined organic layer with magnesium sulfate, removing the solvent with a rotary evaporator, and finally purifying the residual substances with column chromatography with a mixture of dichloromethane and petroleum ether (V: v=1:14) as eluent to obtain a compound shown as an intermediate 2 (yield: 68.15%);
3) At N 2 Under protection, respectively adding an intermediate 2 (1.0 eq), a raw material D (1.1 eq), tetrakis (triphenylphosphine) palladium (0.01 eq) and potassium carbonate (2.0 eq) into a mixed solvent of toluene, ethanol and water, heating to 100 ℃ for reaction for 10 hours, cooling to room temperature after the reaction is finished, after solid precipitation is finished, washing with water to remove salt, leaching with a small amount of ethanol, drying a filter cake, and purifying the residual substance by using a column chromatography with a mixture of dichloromethane and petroleum ether (V: V=1:10) as an eluent to obtain a compound P-20; (yield: 65.21%).
The compound P-20 was assayed as follows:
mass spectrometry test: theoretical value 765.96; the test value was 765.85.
Elemental analysis:
the calculated values are: c,90.95; h,5.13; n,1.83; o,2.09.
The test values are: c,90.68; h,5.28; n,1.95; o,2.16.
Example 3: synthesis of Compound P-118
1) After dissolving the raw material a (1.0 eq) and the raw material B (1.0 eq) in toluene, pd2 (dba) 3 (0.02 eq), P (t-Bu) 3 (0.05 eq) and t-BuONa (2.0 eq) were added under an N2 atmosphere, the temperature was raised to 120 ℃ and stirred for 12 hours, after the reaction was completed, diatomaceous earth was used for hot suction filtration, salts and catalysts were removed, after the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing, an organic phase was retained after separation, an aqueous phase was extracted with ethyl acetate, then the combined organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: v=1:20), to obtain a compound represented by intermediate 1 (yield: 73.21 A) is provided;
2) After intermediate 1 (1.0 eq) and raw material C (1.0 eq) were dissolved in toluene, pd2 (dba) 3 (0.02 eq), P (t-Bu) 3 (0.05 eq) and t-BuONa (2.0 eq) were added under N2 atmosphere, the temperature was raised to 120 ℃ and stirred for reaction for 8h, after the reaction was completed, celite was filtered while hot, salts and catalyst were removed, after the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing, an organic phase was retained after separation, the aqueous phase was extracted with ethyl acetate, then the combined organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator, finally the remaining material was purified by column chromatography with a mixture of dichloromethane and petroleum ether (V: v=1:14), to obtain the compound represented by intermediate 2 (yield: 68.15%).
3) Under the protection of N2, respectively adding an intermediate 2 (1.0 eq), a raw material D (1.1 eq), tetrakis (triphenylphosphine) palladium (0.01 eq) and potassium carbonate (2.0 eq) into a mixed solvent of toluene, ethanol and water, heating to 100 ℃ for reaction for 10 hours, cooling to room temperature after the reaction is finished, washing with water to remove salt after the solid is separated out, eluting with a small amount of ethanol, drying a filter cake, and purifying the residual substance by using a column chromatography with a mixture of dichloromethane and petroleum ether (V: V=1:10) as an eluent to obtain a compound P-118; (yield: 65.20%).
The resulting compound P-118 was subjected to detection analysis, and the results were as follows:
mass spectrometry test: theoretical value 832.08; the test value was 832.28.
Elemental analysis:
the calculated values are: c,89.50; h,4.97; n,1.68; s,3.85.
The test values are: c,89.71; h,5.11; n,1.80; s,3.99.
Examples 4 to 28
The above preparation method can be used to obtain the luminescent auxiliary materials shown in the following table 1;
TABLE 1 summary of the luminescent auxiliary materials prepared in examples 4-28
| Examples | Compounds of formula (I) | Molecular formula | Mass spectrum calculated value | Mass spectrometry test values | Yield (%) |
| Example 4 | P-5 | C 48 H 31 NO | 637.78 | 637.95 | 68.25 |
| Example 5 | P-8 | C 50 H 33 NO | 663.82 | 663.96 | 65.28 |
| Example 6 | P-11 | C 64 H 43 NO | 842.05 | 842.19 | 70.23 |
| Example 7 | P-16 | C 60 H 39 NO | 789.98 | 789.85 | 66.67 |
| Example 8 | P-19 | C 54 H 35 NO | 713.88 | 713.94 | 69.24 |
| Example 9 | P-21 | C 50 H 31 NO 2 | 677.80 | 677.89 | 65.72 |
| Example 10 | P-33 | C 53 H 37 NO 2 | 719.88 | 719.91 | 67.45 |
| Example 11 | P-38 | C 61 H 43 NO 2 | 822.02 | 822.18 | 68.91 |
| Example 12 | P-46 | C 61 H 44 N 2 O | 821.04 | 821.17 | 67.53 |
| Example 13 | P-54 | C 64 H 42 N 2 O | 855.05 | 855.13 | 70.27 |
| Example 14 | P-58 | C 57 H 39 NO 2 | 769.94 | 770.06 | 65.89 |
| Example 15 | P-66 | C 58 H 39 NO | 765.96 | 766.13 | 67.44 |
| Example 16 | P-76 | C 52 H 33 NO 2 | 703.84 | 703.91 | 67.85 |
| Example 17 | P-81 | C 62 H 40 N 2 O | 829.02 | 829.17 | 68.28 |
| Example 18 | P-92 | C 62 H 45 NO 3 | 852.05 | 852.18 | 69.13 |
| Example 19 | P-105 | C 61 H 43 NO 2 | 822.02 | 822.19 | 66.46 |
| Example 20 | P-112 | C 66 H 47 NO 3 | 902.11 | 902.24 | 67.28 |
| Example 21 | P-116 | C 63 H 43 NOS | 862.10 | 862.72 | 68.12 |
| Example 22 | P-121 | C 65 H 45 NOS | 888.14 | 888.23 | 70.17 |
| Example 23 | P-126 | C 61 H 44 N 2 S | 837.10 | 837.26 | 65.75 |
| Example 24 | P-129 | C 62 H 41 NS | 832.08 | 832.27 | 66.81 |
| Example 25 | P-133 | C 58 H 37 NOS | 796.00 | 796.25 | 67.83 |
| Example 26 | P-138 | C 66 H 43 NO | 866.08 | 866.18 | 68.74 |
| Example 27 | P-146 | C 62 H 41 O | 816.02 | 816.24 | 66.19 |
| Example 28 | P-152 | C 73 H 52 N 2 S | 989.29 | 989.33 | 67.18 |
The organic electroluminescent device prepared by adopting the luminescent auxiliary material provided by the embodiment above, when the organic layer comprises the luminescent auxiliary layer, the luminescent auxiliary layer comprises the luminescent auxiliary material provided by the embodiment above.
Device example 1
The preparation of the organic electroluminescent device containing the luminescent auxiliary material specifically 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 forVacuum evaporating cavity injection layer materials HT and P-dock, the chemical formula of which is shown as follows; wherein, the evaporation rate ratio of HT and P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): to be used forVacuum evaporating 120nm HT as a hole transport layer on the hole injection layer;
d. light-emitting auxiliary layer: to be used forVapor-depositing 10nm of the compound P-1 provided in example 1 as a light-emitting auxiliary layer on top of the hole transport layer in vacuo;
e. EML (light emitting layer): then on the light-emitting auxiliary layer toIs a vapor deposition rate of 25nm in thickness (Host) And a doping material (Dopant) as a light emitting layer, the chemical formulas of Host and Dopant thereof are shown below; the evaporation rate ratio of Host to Dopant is 98:2;
f. HB (hole blocking layer): to be used forVacuum evaporating a hole blocking layer with the thickness of 5.0 nm;
g. ETL (electron transport layer): to be used forET and Liq with a thickness of 30nm are vacuum-evaporated as electron transport layers, and the chemical formula of ET is shown below; wherein, the evaporation rate ratio of ET to Liq is 50:50;
h. EIL (electron injection layer): to be used forEvaporating Yb film layer with a thickness of 1.0nm to form an electron injection layer;
i. and (3) cathode: to be used forVapor 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 forCPL with the thickness of 70nm is vacuum deposited on the cathode to be used as a light extraction layer;
k. packaging the substrate subjected to evaporation: 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 related above is as follows:
referring to the method provided in the above device example 1, compounds P-5, P-8, P-11, P-16, P-19, P-20, P-21, P-33, P-38, P-46, P-54, P-58, P-66, P-76, P-81, P-92, P-105, P-112, P-116, P-118, P-121, P-126, P-129, P-133, P-138, P-146, and P-152 were selected as the replacement compounds P-1, respectively, and evaporation of the light-emitting auxiliary layers was performed, to prepare corresponding organic electroluminescent devices, which were respectively denoted as device examples 2 to 28.
Device comparative example 1:
this comparative example provides an organic electroluminescent device whose production method is the only difference from device example 1 in that the organic electroluminescent devices were vapor-deposited using the existing comparative examples 1 to 7, respectively, instead of the light-emitting auxiliary material (compound P-1) in device example 1 described above, to produce device comparative examples 1 to 7. Wherein, the chemical structural formulas of comparative examples 1 to 7 are:
the organic electroluminescent devices containing the light-emitting auxiliary material obtained in the above device examples 1 to 28 and device comparative examples 1 to 7 were characterized in terms of driving voltage, light-emitting efficiency, BI value and lifetime at a luminance of 1000 (nits). The test results are shown in Table 2.
TABLE 2 luminescence property test results (brightness value 1000 nits)
Note that: in the blue top emission device, the current efficiency is greatly affected by chromaticity, so that the ratio of luminous efficiency to CIEy is defined as BI value taking into consideration the factor of chromaticity influence on efficiency.
As can be seen from table 2, the organic electroluminescent devices of examples 1 to 28 prepared using the light-emitting auxiliary materials provided by the present invention were improved in terms of driving voltage, light-emitting efficiency, BI and lifetime as compared with the conventional organic electroluminescent devices provided by comparative examples 1 to 7.
This illustrates: compared with the comparative compound, even if the compound has the same parent nucleus, the hole mobility of the compound can be improved and the space structure can be changed by changing the side chain and prolonging the conjugation of the molecule, so that the compound is more adaptive on the device, and the service life and the luminous efficiency of the OLED device can be effectively improved and the driving voltage can be reduced.
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 (3)
1. A luminescent auxiliary material, characterized by having a structure represented by general formula I:
specifically, the light-emitting auxiliary material is selected from the following structures:
2. a method for preparing a luminescent auxiliary material as claimed in claim 1, characterized in that the method comprises the following steps:
1) After dissolving raw material A and raw material B in toluene, in N 2 Pd addition under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-Buona, heating to 110-120 ℃ and stirring for reaction for 8-12h, filtering with diatomite while the reaction is hot after the reaction is finished, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid to keep an organic phase, extracting the aqueous phase with ethyl acetate, drying the combined organic layer with magnesium sulfate, removing solvent with a rotary evaporator, and finally purifying the rest substances with column chromatography with a mixture of dichloromethane and petroleum ether as eluent to obtain a compound shown as an intermediate 1;
2) Intermediate 1 and starting material C were dissolved in toluene at N 2 Pd addition under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-Buona, heating to 110-120deg.C, stirring for 8-12 hr, filtering with diatomaceous earth, removing salt and catalyst, cooling the filtrate to room temperature, and collecting the filtrateAdding distilled water into the filtrate for washing, separating liquid, retaining an organic phase, extracting an aqueous phase with ethyl acetate, drying the combined organic layers with magnesium sulfate, removing a solvent with a rotary evaporator, and purifying the residual substances with a column chromatography by using a mixture of dichloromethane and petroleum ether as an eluent to obtain a compound shown as an intermediate 2;
3) At N 2 Under the protection, respectively adding the intermediate 2, the raw material D, the tetra (triphenylphosphine) palladium and the potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 90-100 ℃ for reaction for 8-10 hours, cooling to room temperature after the reaction is finished, washing with water to remove salt after the solid is separated out, leaching with a small amount of ethanol, drying a filter cake, and purifying the residual substances by using a column chromatography with a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound shown in the general formula 1;
the specific synthetic route is as follows:
wherein R is 1 、X、L、Ar、Ar 1 And Ar is a group 2 Identical to the above-mentioned representation of the formula I, hal 1 、Hal 2 And Hal 3 Each independently selected from fluorine, chlorine, bromine or iodine.
3. Use of a light-emitting auxiliary material according to claim 1 in an organic electroluminescent device.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016175533A2 (en) * | 2015-04-27 | 2016-11-03 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same, and electronic device comprising same |
| CN112047872A (en) * | 2020-09-18 | 2020-12-08 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent fluorene compound and preparation method and application thereof |
| CN114702432A (en) * | 2022-04-01 | 2022-07-05 | 上海钥熠电子科技有限公司 | Compound containing acenaphthene and application thereof in organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016175533A2 (en) * | 2015-04-27 | 2016-11-03 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same, and electronic device comprising same |
| CN112047872A (en) * | 2020-09-18 | 2020-12-08 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent fluorene compound and preparation method and application thereof |
| CN114702432A (en) * | 2022-04-01 | 2022-07-05 | 上海钥熠电子科技有限公司 | Compound containing acenaphthene and application thereof in organic electroluminescent device |
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