CN115745962B - A condensed heterocyclic compound and its application and an organic electroluminescent device containing the compound - Google Patents
A condensed heterocyclic compound and its application and an organic electroluminescent device containing the compound Download PDFInfo
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims description 46
- 230000000903 blocking effect Effects 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 abstract description 14
- 239000007924 injection Substances 0.000 abstract description 14
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- 239000010410 layer Substances 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 239000010408 film Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 7
- -1 spirobifluorenyl group Chemical group 0.000 description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 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 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- ZGIKWINFUGEQEO-UHFFFAOYSA-N 3-bromoquinoline Chemical compound C1=CC=CC2=CC(Br)=CN=C21 ZGIKWINFUGEQEO-UHFFFAOYSA-N 0.000 description 1
- BYPCJJONRMPERB-UHFFFAOYSA-N C1(=CC(=CC=C1)C1=NC(=NC(=N1)Cl)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC(=CC=C1)C1=NC(=NC(=N1)Cl)C1=CC=CC=C1)C1=CC=CC=C1 BYPCJJONRMPERB-UHFFFAOYSA-N 0.000 description 1
- 102100037373 DNA-(apurinic or apyrimidinic site) endonuclease Human genes 0.000 description 1
- 101710109420 DNA-(apurinic or apyrimidinic site) endonuclease Proteins 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
本发明提供了一种稠合杂环类化合物及其应用，以及包含该化合物的有机电致发光器件。通过调节电子迁移率和增强电子注入能力，使得保持器件效率的前提下，降低工作电压、提高器件寿命，从而解决了现有技术中器件驱动电压高、效率低的问题。
The present invention provides a fused heterocyclic compound and its application, as well as an organic electroluminescent device containing the compound. By adjusting the electron mobility and enhancing the electron injection capability, the operating voltage is reduced and the device life is increased while maintaining the device efficiency, thereby solving the problem of high device driving voltage and low efficiency in the prior art.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound and application thereof, and an organic electroluminescent device containing the compound.
Background
An Organic electroluminescent device (OLED: organic LIGHT EMITTING DEVICES) is a current-driven thin film device similar to a sandwich structure, and a single layer or multiple layers of Organic functional material are sandwiched between an anode and a cathode. The OLED has the characteristics of self-luminescence, wide visual angle, wide color gamut, short response time, high luminous efficiency, low working voltage, low cost, simple production process and the like, and is widely applied to display products such as televisions, smart phones, tablet computers, vehicle-mounted display, illumination and the like, and further applied to creative display products such as large-size display and flexible screens.
The organic photoelectric material applied to the OLED device may be classified into a light emitting layer material and an auxiliary functional layer material in use, wherein the light emitting layer material includes a guest material (also referred to as a light emitting material, a doping material) and a host material (also referred to as a host material), the light emitting material is classified into a fluorescent material, a phosphorescent material and a thermally activated delayed fluorescent material according to different energy transfer modes, and the auxiliary functional layer material is classified into an electron injecting material, an electron transporting material, a hole blocking material, an electron blocking material, a hole transporting material and a hole injecting material according to different properties of electron or hole transporting speed.
The electron transport materials generally have proper HOMO/LUMO values, so that the driving voltage can be reduced due to the fact that smaller electron injection potential barriers are adopted, meanwhile, higher electron transport rate, higher glass transition temperature and higher thermal stability are required, common electron injection materials in the industry such as azole derivatives, quinoline derivatives and metal chelates are required, but some materials are easy to crystallize and easily cause shorter service life of devices, and some materials cannot be effectively matched with HOMO/LUMO of adjacent functional layer materials due to overlarge energy gaps, so that energy cannot be fully utilized, the injection potential barriers are too high, and the devices have the problems of overhigh driving voltage and lower efficiency.
Therefore, there is a need in the art to develop an OLED electron transport material that can produce an organic electroluminescent device with high efficiency and long lifetime at low driving voltages.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel organic compound, in particular to:
1) A condensed heterocyclic compound for an organic electroluminescent device, wherein the compound is represented by formula (1):
A-C-B
(1)
Wherein the A unit has a structure shown in formula (A):
the B unit has a structure shown in a formula (B):
wherein-represents the connection position between the units;
The C unit is naphthylene;
Wherein L in the formula (A) can be selected from a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 50 ring-forming carbon atoms, Y 1 to Y 3 are the same or different from each other and each independently is an N atom or CH, and at least one of Y 1 to Y 3 is an N atom, ar 1 and Ar 2 are the same or different from each other and each independently is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms;
Wherein Y 4 to Y 6 in the formula (B) are the same or different from each other and are each independently an N atom or CR 1, and at least one of Y 4 to Y 6 is an N atom, R 1 is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
2) The condensed heterocyclic compound for an organic electroluminescent device according to 1), wherein L is selected from a single bond, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted carbazolyl group.
3) The condensed heterocyclic compound for an organic electroluminescent device according to 1), wherein the Ar 1 and Ar 2 are each independently selected from the group consisting of a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted carbazolyl group.
4) The condensed heterocyclic compound for an organic electroluminescent device according to 1), wherein the compound is represented by formula (2):
Wherein Ar 1、Ar2, L, C units, Y 4 to Y 6 are as defined in 1).
5) The condensed heterocyclic compound for an organic electroluminescent device according to 1), wherein the condensed heterocyclic compound is selected from the following structures:
6) An organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode and at least one layer of organic film between the anode and the cathode, wherein the organic film contains the compound of any one of 1) to 5).
7) The organic electroluminescent device according to 6), wherein the compound is applied as an electron transport material or a hole blocking material in the organic electroluminescent device.
Compared with the prior art, the invention has the beneficial effects that:
By adjusting the electron mobility and enhancing the electron injection capability, the working voltage is reduced and the service life of the device is prolonged on the premise of keeping the efficiency of the device, so that the problems of high driving voltage and low efficiency of the device in the prior art are solved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
FIG. 1 is a schematic diagram of an organic electroluminescent device to which the compound of the present invention is applied, wherein the structure of each layer of the device is represented as follows:
1. transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer A,5, hole transport layer B (or electron blocking layer), 6, luminescent layer, 7, electron transport layer B (or hole blocking layer), 8, electron transport layer A,9, electron injection layer, 10, cathode reflection electrode layer.
Detailed Description
The principles and features of the present invention will be further illustrated by the following examples of various synthetic embodiments, which are provided for purposes of illustration only and are not intended to limit the scope of the invention.
A method for synthesizing the specific compound of formula (1) listed below.
Synthesis example 1 Synthesis of chemical formula 2
Synthesis of intermediate 1a:
4.16g (20 mmol,1.0 eq) of 2-bromoquinoline, 4.55g (22 mmol,1.1 eq) of 4-chloro-1-naphthaleneboric acid, 0.46g (0.4 mmol,0.02 eq) of palladium tetrakis triphenylphosphine, 5.5g (40 mmol,2.0 eq) of potassium carbonate were weighed into the flask, the flask was purged with nitrogen, deoxygenated with 50ml of dioxane, and 10ml of water were added and the reaction was refluxed at 80℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, and separating with a silica gel column to obtain 5.33g of white solid 1a with a yield of 92%, and a mass spectrum with a molecular weight of M/z= 289.9 (m+h) + was measured
Synthesis of chemical formula 2:
2.90g (10 mmol,1.0 eq) of intermediate 1a,4.79g (11 mmol,1.1 eq) 1b,0.18g (0.20 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.36g (0.80 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.75g (20 mmol,2.0 eq) of potassium carbonate are weighed into the flask, the flask is purged with gas, nitrogen protected, deoxygenated 50ml of dioxane is added, and 10ml of water are added, and the reaction is refluxed at 100℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 4.61g of white solid 2 in 81% yield with a mass spectrum having a molecular weight of M/z=563.1 (m+h) + molecular weight of M/z=563.1
Synthesis example 2 Synthesis of chemical modification 11
Synthesis of intermediate 2a:
4.16g (20 mmol,1.0 eq) of 3-bromoquinoline, 4.55g (22 mmol,1.1 eq) of 4-chloro-1-naphthaleneboric acid, 0.46g (0.4 mmol,0.02 eq) of palladium tetrakis triphenylphosphine, 5.5g (40 mmol,2.0 eq) of potassium carbonate were weighed into the flask, the flask was purged with nitrogen, deoxygenated with 50ml of dioxane, and 10ml of water were added and the reaction was refluxed at 80℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, and separating with a silica gel column to obtain 5.28g of white solid 2a with a yield of 90%, and a mass spectrum with a molecular weight of M/z= 289.9 (m+h) + was measured
Synthesis of chemical formula 11:
2.90g (10 mmol,1.0 eq) of intermediate 2a,4.78g (11 mmol,1.1 eq) of 2, 4-diphenyl-6- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine, 0.18g (0.20 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.36g (0.80 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.75g (20 mmol,2.0 eq) of potassium carbonate are weighed into the flask, the flask is purged, nitrogen protected, deoxygenated 50ml of dioxane is added, and 10ml of water are added and the reaction is carried out under reflux at 100℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 4.90g of white solid 11 in 87% yield, mass spectrometry with a molecular weight of M/z= 563.3 (m+h) + in terms of weight
Synthesis example 3 Synthesis of chemical modification 13
2.90G (10 mmol,1.0 eq) of intermediate 1a,4.78g (11 mmol,1.1 eq) 2, 4-diphenyl-6- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine, 0.18g (0.20 mmol,0.02 eq) tris (dibenzylideneacetone) dipalladium, 0.36g (0.80 mmol,0.08 eq) 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.75g (20 mmol,2.0 eq) potassium carbonate were weighed into the flask, purged with nitrogen, deoxygenated 50ml dioxane was added, and 10ml water were reacted at 100℃for 12h under reflux. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 4.73g of white solid 13 in 84% yield, with a molecular weight of M/z= 563.3 (m+h) + as determined by mass spectrometry
Synthesis example 4 Synthesis of chemical modification 24
Synthesis of intermediate 4a:
6.86g (20 mmol,1.0 eq) of 2- ([ 1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine, 4.4g (22 mmol,1.1 eq) of 4-bromophenylboronic acid, 0.46g (0.4 mmol,0.02 eq) of tetrakis triphenylphosphine palladium, 5.5g (40 mmol,2.0 eq) of potassium carbonate were weighed into the flask, the flask was purged with nitrogen, 100ml of tetrahydrofuran deoxygenated, and 20ml of water were added and the reaction was refluxed at 80℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, and separating with a silica gel column to obtain 7.78g of white solid 4a with a yield of 84%, and a mass spectrum with a molecular weight of M/z=464.1 (m+h) + was measured
Synthesis of intermediate 4 b:
4.64g (10 mmol,1.0 eq) of intermediate 4a,3.05g (12 mmol,1.2 eq) of bisboronic acid pinacol ester, 0.22g (0.30 mmol,0.03 eq) of [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride, 0.2g (20 mmol,2.0 eq) of potassium acetate are weighed into a flask, purged with nitrogen, deoxygenated with 50ml of dioxane and reacted at 100℃under reflux for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 3.98g of a white solid in 78% yield, the mass spectrum of which shows a molecular weight of M/z=511.8 (m+h) + Synthesis of 24
2.90G (10 mmol,1.0 eq) of intermediate 2a,5.6g (11 mmol,1.1 eq) of intermediate 4b,0.18g (0.20 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.36g (0.80 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.75g (20 mmol,2.0 eq) of potassium carbonate are weighed into the flask, the flask is purged with nitrogen, deoxygenated with 150ml of dioxane and 30ml of water are added, and the reaction is carried out under reflux at 100℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 5.81g of white solid 24 in 91% yield, and the molecular weight by mass spectrometry is M/z= 639.3 (m+h) + with a total of
Synthesis example 5 Synthesis of chemical modification 56
Synthesis of intermediate 5 a:
3.56g (10 mmol,1.0 eq) of 2- (9H-carbazole) -4-chloro-6-phenyl-1, 3, 5-triazine, 2.2g (11 mmol,1.1 eq) of 4-bromophenylboronic acid, 0.23g (0.2 mmol,0.02 eq) of tetrakis triphenylphosphine palladium, 2.75g (20 mmol,2.0 eq) of potassium carbonate were weighed into the flask, the flask was purged, nitrogen protected, 60ml of tetrahydrofuran with oxygen removed, and 15ml of water were added, and the reaction was refluxed at 70℃for 12 hours. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, and separating with a silica gel column to obtain 4.29g of white solid 4a with a yield of 90%, and a mass spectrum with a molecular weight of M/z=476.8 (m+h) + was determined
Synthesis of intermediate 4 b:
4.77g (10 mmol,1.0 eq) of intermediate 4a,3.05g (12 mmol,1.2 eq) of bisboronic acid pinacol ester, 0.22g (0.30 mmol,0.03 eq) of [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride, 0.2g (20 mmol,2.0 eq) of potassium acetate are weighed into a flask, purged with nitrogen, deoxygenated 80ml of dioxane are added and the reaction is carried out at 100℃for 12h under reflux. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 4.15g of a white solid with a yield of 79% and a mass spectrum of molecular weight M/z=524.8 (m+h) + synthesis of 56
2.90G (10 mmol,1.0 eq) of intermediate 1a,5.78g (11 mmol,1.1 eq) of intermediate 4b,0.18g (0.20 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.36g (0.80 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.75g (20 mmol,2.0 eq) of potassium carbonate were weighed into the flask, vented, nitrogen-protected, deoxygenated in 150ml of dioxane, and 30ml of water were added and the reaction was refluxed at 100℃for 12h. Stopping the reaction, cooling to room temperature, extracting with ethyl acetate, washing with water three times, concentrating the solvent, recrystallizing with ethyl acetate to give 5.61g of white solid 56 in 86% yield, and the molecular weight by mass spectrometry is M/z= 652.3 (m+h) + with a molecular weight of
Device embodiment fabrication of organic electroluminescent device used as electron transport Material
A glass substrate having a thickness of 25mm by 75mm by 1.1mm and having an Indium Tin Oxide (ITO) transparent electrode (anode) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then Ultraviolet (UV) -ozone cleaned for 30 minutes. The film thickness of ITO was 130nm. The cleaned glass substrate was mounted on a substrate holder of a vacuum deposition apparatus, and vacuum was applied to 1×10 -5～1×10-6 Pa, and a Hole Injection Layer (HIL) HATCN was deposited on the ITO transparent conductive layer to a film thickness of 15nm. A hole transport layer A (HTL) was deposited on the hole injection layer to a film thickness of 60nm. Then, an Electron Blocking Layer (EBL) was deposited on top of the hole transport layer A, with a film thickness of 5nm. Then, an electron blocking layer (EML) was co-deposited on the electron blocking layer to a film thickness of 20nm. The light-emitting layer (EML) was vapor-deposited with a light-emitting material BD and a host material BH of the light-emitting layer by means of multi-source co-vapor deposition, wherein the doping concentration of the light-emitting material was 2 wt%. In order to ensure the accuracy of the doping concentration of the luminescent material, the shielding partition plate is opened after the evaporation rates of the luminescent material and the main material are stable, and the multisource co-evaporation is performed. Then, a Hole Blocking Layer (HBL) was deposited on the light-emitting layer to form 7a film having a thickness of 5nm. Then, an electron transport material (ETL) and lithium 8-hydroxyquinoline (Liq) were vapor deposited on the hole blocking layer, with a film thickness of 30nm and a doping ratio of 1:1. An electron injection Electrode (EIL) was deposited on the ETL to have a film thickness of 1nm. Then, metal cathode aluminum (Al) was deposited on the EIL to have a film thickness of 100nm. The structure of the organic electroluminescent device of example 1 is shown in fig. 1, and fig. 1 also shows the stacking sequence and effect of each functional layer.
The OLED has in principle a layer structure of a substrate/Hole Injection Layer (HIL)/hole injection layer (HTL)/Electron Blocking Layer (EBL)/light emitting layer (EML)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL) and finally a cathode. The cathode is formed of an aluminum layer having a thickness of 100 nm. The molecular structure of the materials for the OLED is shown in table 1.
Table 1 materials for OLED
Device examples 1 to 5 production of organic electroluminescent devices as electron transport materials
TABLE 2 Compounds of the invention used in electron transport layers for device examples
The device structure of device example 1 is specifically ITO (130)/HATCN (15)/HTL (60)/EBL (5)/BH: BD (20, wt% 2)/HBL (5)/Liq (30, wt% 50)/Liq (1)/Al (100), and it should be noted that numbers in brackets indicate film thickness (units: nm).
Device examples 2-5 differ from device example 1 only in that the inventive compound 2 used in the electron transport layer was replaced with another inventive compound, as detailed in table 4.
Comparative examples 1 to 3:
TABLE 3 comparative examples Compounds for use in electron transport layers
Comparative examples 1 to 3 are different from example 1 in that the electron transport layer materials in the organic electroluminescent devices were changed to REF-1 to REF-3 having similar structures reported in the industry, and the resulting device performance test data are shown in table 4.
The OLED was characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), is determined, which is calculated as a function of the luminescence density from the current/voltage/luminescence density characteristic line (IUL characteristic line) exhibiting lambertian emission characteristics. The required voltage V1000 is determined at a luminance of 1000cd/m 2. CE1000 represents the current efficiency achieved at a luminance of 1000cd/m 2. Finally, EQE1000 represents the external quantum efficiency at an operating luminance of 1000cd/m 2, and T95 represents the operating time for the device to fade to 95% at an initial luminance of 1000cd/m 2.
TABLE 4 Table 4
As can be seen from table 4, compared with the prior art, the device embodiments 1 to 5 of the present invention can reduce the driving voltage and increase the lifetime of the device while maintaining the current efficiency of the OLED. The driving voltage V1000 of device example 2, in which the voltage was shown to be 11, was reduced from 4.1V to 3.7V, and more importantly, the device lifetime T95 was increased by 56.7% as compared to comparative example 2. The protection material is mainly characterized in that the protection material is prepared by connecting the A unit and the B unit at specific positions through the naphthalene unit, so that the mobility of the material can be effectively regulated, the electron injection barrier can be reduced, the driving voltage can be reduced, and the service life of a device can be prolonged.
Claims (3)
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