CN116262745A - 1,2, 4-triazole compound, preparation method thereof and electroluminescent device - Google Patents
1,2, 4-triazole compound, preparation method thereof and electroluminescent device Download PDFInfo
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- -1 1,2, 4-triazole compound Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000010992 reflux Methods 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- 125000005842 heteroatom Chemical group 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 230000000903 blocking effect Effects 0.000 claims description 19
- 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 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 125000005549 heteroarylene group Chemical group 0.000 claims description 16
- 125000000732 arylene group Chemical group 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 10
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 229910052722 tritium Inorganic materials 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 7
- 241000720974 Protium Species 0.000 claims description 7
- 125000002541 furyl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000005551 pyridylene group Chemical group 0.000 claims description 4
- 125000006836 terphenylene group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 36
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 2
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- 239000011259 mixed solution Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 18
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- 238000001816 cooling Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
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- 229910002027 silica gel Inorganic materials 0.000 description 8
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical compound FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention belongs to the technical field of semiconductors, and particularly relates to a 1,2, 4-triazole compound, a preparation method thereof and an electroluminescent device. The 1,2, 4-triazole compound provided by the invention has a structure shown in a formula I, and the compound takes 1,2, 4-triazole as a core, has stronger structural rigidity, and improves the structural stability of materials; in the space structure, the three branched chains extend to three directions, so that the material has better planeness and higher obtainingRefractive index of (2); meanwhile, the mutual accumulation of molecules is avoided, so that the 1,2, 4-triazole compound provided by the invention has high molecular thermal stability. The 1,2, 4-triazole compound provided by the invention has low absorption and high refractive index in the visible light field, and the OLED device prepared by taking the 1,2, 4-triazole compound provided by the invention as the light extraction layer has higher light extraction efficiency.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a 1,2, 4-triazole compound, a preparation method thereof and an electroluminescent device.
Background
With the development of technology, the OLED display technology has been widely applied to the fields of smart phones, tablet computers, and the like. However, a large gap exists between the external quantum efficiency and the internal quantum efficiency of the traditional OLED device, so that the OLED device has lower light-emitting efficiency, and the development and application fields of the OLED are severely restricted.
At present, the method for improving the light-emitting efficiency of the OLED device mainly comprises the steps of forming folds on the light-emitting surface of a substrate, adding photonic crystals, micro-lens array (MLA) structures or adding a surface light extraction layer. Wherein, forming wrinkles or adding photonic crystals on the light-emitting surface of the substrate can improve the light-emitting efficiency of the OLED device, but can affect the radiation spectrum angular distribution of the OLED, thereby affecting the performance of the OLED device. The surface light extraction layer is added on the surface of the substrate, so that the light extraction efficiency of the OLED device can be improved while the performance of the OLED device is ensured, the material for preparing the light extraction layer is a light extraction material, the existing light extraction material has limited improvement on the light extraction efficiency of the OLED device, and most of the existing light extraction material is 20%, so that development of the light extraction material capable of greatly improving the light extraction efficiency of the OLED device is needed.
Disclosure of Invention
In view of the above, the invention provides a 1,2, 4-triazole compound, a preparation method thereof and an electroluminescent device, and the light extraction layer of the electroluminescent device is prepared by using the 1,2, 4-triazole compound provided by the invention, so that the light extraction efficiency of the OLED device can be effectively improved.
In order to solve the technical problems, the invention provides a 1,2, 4-triazole compound which has a structure shown as a formula I:
wherein L is 1 、L 2 、L 3 Independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms;
Ar 1 、Ar 2 、Ar 3 independently is a structure shown in any one of formulas 2-6, and Ar 1 、Ar 2 And Ar is a group 3 At least one of them is a group of the structure shown in formula 2:
wherein X is-O-, -S-or-NR-, R is C 1 ～C 10 An alkyl group of (a) a substituted or unsubstituted 6-to 30-membered aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group;
R 1 、R 2 、R 3 、R 4 independently hydrogen, deuterium, tritium, halogen, cyano, C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, and when R 1 、R 2 、R 3 、R 4 R when they are each a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms 1 、R 2 、R 3 、R 4 Respectively connected with the parallel rings of the formulas 2, 3 and 4;
L 4 、L 5 independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms;
R 5 、R 6 independently C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 Alkoxy of (C)Substituted or unsubstituted 6-30 membered aryl or substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms;
R 7 a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the heteroatoms in the heteroaryl and heteroarylene groups are independently oxygen, sulfur or nitrogen;
the substituents in the substituted aryl, substituted heteroaryl, substituted arylene and substituted heteroarylene are independently protium, deuterium, tritium, halogen, cyano and C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6 to 20 membered aryl group, or a substituted or unsubstituted 5 to 20 membered heteroaryl group containing one or more heteroatoms.
The 1,2, 4-triazole compound provided by the invention takes 1,2, 4-triazole as a core, has stronger structural rigidity, and improves the structural stability of the material; according to the 1,2, 4-triazole compound provided by the invention, three branched chains extend to three directions on the space structure, so that the material has better planeness and higher refractive index is obtained; meanwhile, the mutual accumulation of molecules is avoided, so that the 1,2, 4-triazole compound provided by the invention has high molecular thermal stability. The 1,2, 4-triazole compound provided by the invention has low absorption and high refractive index in the visible light field, and the OLED device prepared by taking the 1,2, 4-triazole compound provided by the invention as the light extraction layer has higher light extraction efficiency.
Drawings
Fig. 1 is a schematic structural diagram of an electroluminescent device prepared in an embodiment, in which 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking layer/electron transport layer, 8 is an electron injection layer, 9 is a cathode layer, and 10 is a light extraction layer.
Detailed Description
The invention provides a 1,2, 4-triazole compound which has a structure shown as a formula I:
in the present invention, the 1,2, 4-triazole compound preferably has a structure as shown in any one of formulas I-1 to I-34:
in the present invention, the numbers in formulas I-1 to I-34 represent substitutable sites.
In the present invention, the 1,2, 4-triazole compound preferably has a structure as shown in formulas I-37 to I-39:
in the invention, the 1,2, 4-triazole compound has a structure shown in the formulas I-40 to I-41:
in the present invention, L 1 、L 2 、L 3 Independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms; the L is 1 、L 2 And L 3 Independently preferred are a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazole group, or a substituted or unsubstituted dibenzofuranylene group. In the present invention, L 2 Preferably a single bond, a substituted or unsubstituted 6-to 20-membered arylene, a substituted or unsubstituted 5-to 20-membered heteroarylene containing one or more heteroatoms; l (L) 1 、L 3 Independently preferred are substituted or unsubstituted 6-20 membered arylene, substituted or unsubstituted 5-20 membered heteroarylene containing one or more heteroatoms.
In the present invention, ar 1 、Ar 2 、Ar 3 Independently is a structure shown in any one of formulas 2-6, and Ar 1 、Ar 2 And Ar is a group 3 At least one of them is a group of the structure shown in formula 2:
in the present invention, X is-O-, -S-or-NR-; r is C 1 ～C 10 Substituted or unsubstituted 6-to 30-membered aryl, substituted or unsubstituted 5-to 30-membered heteroaryl, preferably methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl or substituted or unsubstituted biphenyl;
in the present invention, R 1 、R 2 、R 3 、R 4 Independently hydrogen, deuterium, tritium, halogen, cyano, C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, and when R 1 、R 2 、R 3 、R 4 Are each a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatomsR is a radical 1 、R 2 、R 3 、R 4 Respectively connected with the parallel rings of the formulas 2, 3 and 4; independently preferred are hydrogen, protium, deuterium, tritium, halogen, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridinyl, or substituted or unsubstituted furanyl.
In the present invention, L 4 、L 5 Independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms; independently preferred are a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazole group, or a substituted or unsubstituted dibenzofuranylene group.
In the present invention, R 5 、R 6 Independently C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6 to 30 membered aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group containing one or more heteroatoms; independently preferred are methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted dibenzothiophenyl or substituted or unsubstituted dibenzofuranyl.
In the present invention, R 7 Substituted or unsubstituted 5-to 30-membered heteroatomic groups containing one or more hetero atoms for substituted or unsubstituted 6-to 30-membered aryl groupsAn aryl group; preferred are a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted dibenzofuranyl group.
In the present invention, the heteroatoms in the heteroaryl and heteroarylene are independently oxygen, sulfur or nitrogen, preferably oxygen or nitrogen. In the present invention, the substituents in the substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene are independently protium, deuterium, tritium, halogen, cyano, C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 Independently is preferably protium, deuterium, tritium, cyano, fluorine, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, naphthyridinyl, biphenyl, terphenyl, pyridinyl, carbazolyl or dibenzofuranyl.
In the invention, the 1,2, 4-triazole compound has a structure shown in any one of the following structural formulas:
the invention also provides a preparation method of the 1,2, 4-triazole compound, which comprises the following steps:
mixing a substance with a structure shown in a formula a, a substance with a structure shown in a formula b, tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a first organic solvent, and performing a first reflux reaction to obtain a first intermediate;
mixing the first intermediate, a substance with a structure shown in a formula c, tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a second organic solvent, and performing a second reflux reaction to obtain a second intermediate;
mixing the second intermediate, a substance with a structure shown in a formula d, a third organic solvent, tris (dibenzylideneacetone) dipalladium and tris (tertiary butyl) phosphine for a third reflux reaction to obtain a 1,2, 4-triazole compound with a structure shown in a formula I;
the invention mixes a substance with a structure shown in a formula a, a substance with a structure shown in a formula b, tetra (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a first organic solvent, and carries out a first reflux reaction to obtain a first intermediate. In the present invention, the mixing preferably includes the steps of:
dissolving a substance with a structure shown in a formula a and a substance with a structure shown in a formula b in a first organic solvent to obtain a first mixed solution;
to the first mixed solution, tetrakis (triphenylphosphine) palladium and an aqueous potassium carbonate solution were added.
In the present invention, the first organic solvent is preferably Tetrahydrofuran (THF). The amount of the first organic solvent is not particularly limited as long as the material can be completely dissolved. In the present invention, the molar ratio of the substance having the structure represented by formula a to the substance having the structure represented by formula b is preferably 1:0.4 to 0.6, more preferably 1:0.5.
In the present invention, the molar concentration of the aqueous potassium carbonate solution is preferably 2.8 to 3.2mol/L, more preferably 3mol/L. The dosage of the aqueous solution of potassium carbonate is not particularly limited, and the aqueous solution of potassium carbonate is prepared according to the conventional dosage proportion. In the present invention, the substance having the structure represented by formula a and tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The molar ratio of (2) is preferably 1:7 to 10, more preferably 7.5 to 8.
In the present invention, the temperature of the first reflux reaction is determined according to the first organic solvent. In the present invention, the time of the first reflux reaction is preferably 8 to 12 hours. In the present invention, the first reflux reaction is preferably performed under a protective atmosphere, which is preferably nitrogen or argon, more preferably nitrogen. The present invention preferably uses a spot-plating method to determine the end point of the first reflow reaction.
In the present invention, the first reflux reaction further preferably includes: and cooling the system after the first reflux reaction, filtering, concentrating the filtrate obtained by filtering, and purifying through a silica gel column to obtain a first intermediate. In the present invention, the cooling is preferably air cooling, and the temperature of the cooled system is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. In the present invention, the filtration is preferably performed through a pad of celite; the present invention preferably uses chloroform for washing during the filtration process. In the present invention, the concentration is preferably vacuum evaporation. The invention removes most of the solvent in the filtrate through concentration, and the invention has no special requirement on the concentration time, so long as the most of the solvent in the filtrate can be removed. The method has no special requirement on the way of passing through the silica gel column, and can be carried out by adopting a conventional way in the field; the present invention preferably uses a hexane-toluene mixture as the eluent.
In the present invention, the first intermediate has a structure as shown in formula e:
after the first intermediate is obtained, the first intermediate, a substance with a structure shown in a formula c, tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a second organic solvent are mixed, and a second reflux reaction is carried out to obtain a second intermediate. In the present invention, the mixing preferably includes the steps of:
dissolving a first intermediate and a substance with a structure shown in a formula c in a second organic solvent to obtain a second mixed solution;
to the second mixed solution, tetrakis (triphenylphosphine) palladium and an aqueous potassium carbonate solution were added.
In the present invention, the second organic solvent is preferably Tetrahydrofuran (THF). The amount of the second organic solvent used in the present invention is not particularly limited as long as the material can be completely dissolved. In the present invention, the molar ratio of the first intermediate to the substance having the structure represented by formula c is preferably 1:0.5 to 1, more preferably 1:1.
In the present invention, the molar concentration of the aqueous potassium carbonate solution is preferably 2.8 to 3.2mol/L, more preferably 3mol/L. The dosage of the aqueous solution of potassium carbonate is not particularly limited, and the aqueous solution of potassium carbonate is prepared according to the conventional dosage proportion. In the present invention, the first intermediateAnd tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The molar ratio of (2) is preferably 1:7 to 10, more preferably 7.5 to 8.
In the present invention, the temperature of the second reflux reaction is preferably determined according to the second organic solvent. In the present invention, the time of the second reflux reaction is preferably 15 to 17 hours, more preferably 16 hours. In the present invention, the second reflux reaction is preferably performed under a protective atmosphere, which is preferably nitrogen or argon, more preferably nitrogen. The present invention preferably uses the spot-plating method to determine the end point of the second reflow reaction.
In the present invention, the second reflux reaction further preferably includes: and cooling the second reflux reaction system, filtering, concentrating the filtrate obtained by filtering, and purifying by a silica gel column to obtain a second intermediate. In the present invention, the cooling is preferably air cooling, and the temperature of the cooled system is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. In the present invention, the filtration is preferably performed through a pad of celite; the present invention preferably uses chloroform for washing during the filtration process. In the present invention, the concentration is preferably vacuum evaporation. The invention removes most of the solvent in the filtrate through concentration, and the invention has no special requirement on the concentration time, so long as the most of the solvent in the filtrate can be removed. The method has no special requirement on the way of passing through the silica gel column, and can be carried out by adopting a conventional way in the field; the present invention preferably uses a hexane-toluene mixture as the eluent.
In the present invention, when the substance having the structure represented by formula b and the substance having the structure represented by formula c are the same substance, the present invention preferably combines the first reflux reaction and the second reflux reaction, except that the molar amount of the material is added in accordance with the structure of the second intermediate.
In the present invention, the second intermediate has a structure represented by formula f:
after the second intermediate is obtained, the second intermediate, a substance with a structure shown in a formula d, a third organic solvent, tris (dibenzylideneacetone) dipalladium and tris (tertiary butyl) phosphine are mixed for a third reflux reaction, and the 1,2, 4-triazole compound with the structure shown in the formula I is obtained. In the present invention, the mixing preferably includes the steps of:
dissolving the second intermediate and a substance with a structure shown in a formula d in a third organic solvent to obtain a third mixed solution;
to the third mixed solution, tris (dibenzylideneacetone) dipalladium and tris (t-butyl) phosphine were added.
In the present invention, the third organic solvent is preferably toluene. The amount of the third organic solvent used in the present invention is not particularly limited as long as the material can be completely dissolved. In the present invention, the molar ratio of the second intermediate to the substance having the structure represented by formula d is preferably 1:1 to 2, more preferably 1:1 to 1.5.
In the present invention, the second intermediate and (Pd 2 (dba) 3 ) Preferably 1:3×10 -3 ～5×10 -3 . In the present invention, the second intermediate and tri (t-butyl) phosphine (P (t-Bu) 3 ) Preferably 1:3×10 -3 ～5×10 -3 。
In the present invention, the temperature of the third reflux reaction is preferably 100 to 120 ℃, more preferably 110 to 120 ℃; the time of the third reflux reaction is preferably 20 to 24 hours, more preferably 22 to 24 hours. In the present invention, the third reflux reaction is preferably performed under a protective atmosphere, which is preferably nitrogen or argon, more preferably nitrogen. The present invention preferably uses TLC to determine the end point of the third reflux reaction.
In the present invention, the third reflux reaction further preferably includes: and cooling the system after the third reflux reaction, filtering, and rotationally steaming the filtrate obtained by filtering and passing through a neutral silica gel column to obtain the 1,2, 4-triazole compound with the structure shown in the formula I. In the present invention, the cooling is preferably air cooling, and the temperature of the cooled system is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. The invention has no special requirement on the filtration, and can be realized by adopting a conventional mode in the field. The invention removes the solvent in the filtrate through rotary evaporation, and the invention has no special requirement on the rotary evaporation, so long as the solvent in the filtrate can be removed. The method has no special requirement on the way of passing through the neutral silica gel column, and can be carried out by adopting the conventional way in the field.
The invention also provides the application of the 1,2, 4-triazole compound in the technical scheme or the 1,2, 4-triazole compound prepared by the preparation method in the technical scheme in an electroluminescent device.
The invention also provides an electroluminescent device, which comprises a substrate, a first electrode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer/electron transport layer, an electron injection layer, a second electrode layer and a light extraction layer which are sequentially laminated, wherein the light extraction layer is prepared from the 1,2, 4-triazole compound prepared by the technical scheme or the 1,2, 4-triazole compound prepared by the preparation method.
In the present invention, the electroluminescent device includes a substrate. In the present invention, the substrate preferably includes a transparent substrate or an opaque substrate; the transparent substrate is preferably glass or transparent plastic, more preferably glass; the opaque substrate is preferably a silicon substrate. The invention determines the use direction of the substrate according to different mechanical strength, thermal stability, transparency, surface smoothness and waterproofness of the substrate.
In the present invention, the electroluminescent device includes a first electrode layer. In the present invention, the first electrode in the first electrode layer is preferably an anode. In the present invention, the first electrode is preferably a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. In the present invention, when the first electrode is a transmissive electrode, the first electrode is preferably formed of a transparent metal oxide; the transparent metal oxide is preferably Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide (ZnO), or Indium Tin Zinc Oxide (ITZO). In the present invention, when the first electrode is a semi-transmissive electrode or a reflective electrode, the first electrode is preferably one or more of Ag, mg, al, pt, pd, au, ni, nd, ir and Cr. In the present invention, the thickness of the first electrode layer is preferably 50 to 500nm.
In the present invention, the electroluminescent device includes a hole injection layer. In the present invention, the thickness of the hole injection layer is preferably 5 to 100nm. The method for obtaining the hole injection layer is not particularly limited, and a conventional method in the art can be adopted.
In the present invention, the electroluminescent device includes a hole transport layer. In the present invention, the thickness of the hole transport layer is preferably 5 to 200nm. The hole transport layer is not particularly limited, and may be obtained by a conventional method in the art.
In the present invention, the electroluminescent device includes an electron blocking layer. In the present invention, the thickness of the electron blocking layer is preferably 1 to 50nm. The method for obtaining the electron blocking layer is not particularly limited, and a conventional method in the field can be adopted.
In the present invention, the electroluminescent device includes a light emitting layer. In the present invention, the light emitting layer preferably includes a host material, which is a green host material common in the art, and a doping material, which is a doping material common in the art. In the present invention, the host material is preferably a single host material or a double host material. In the present invention, the thickness of the light emitting layer is preferably 5 to 50nm. The invention can adjust the thickness of the light emitting layer to optimize the light emitting efficiency and the driving voltage.
In the present invention, the electroluminescent device comprises a hole blocking layer/electron transport layer. In the present invention, the hole blocking layer/electron transport layer is a hole blocking layer or an electron transport layer. In the present invention, the hole blocking layer material may be a hole blocking layer material for an organic electroluminescent device, which is well known in the art. In the present invention, the thickness of the hole blocking layer is preferably 2 to 200nm. In the present invention, the electron transport layer material is a material that easily receives electrons of a cathode and transfers the received electrons to a light emitting layer, and has high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials for organic electroluminescent devices known in the art may be used. In the present invention, the thickness of the electron transport layer is preferably 10 to 80nm.
In the present invention, the electroluminescent device includes an electron injection layer. In the present invention, the electron injection layer material is preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art can be used. In the present invention, the thickness of the electron injection layer is preferably 0.1 to 5nm.
In the present invention, the electroluminescent device includes a second electrode layer. In the present invention, the second electrode in the second electrode layer is preferably a cathode. In the present invention, the second electrode is preferably a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode preferably comprises Li, yb, ca, liF/Ca, liF/Al, al, mg, baF, ba, ag or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode preferably comprises Ag, mg, yb, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti or a compound or mixture thereof. In the present invention, the thickness of the second electrode layer is preferably dependent on the material used.
In the present invention, the electroluminescent device includes a light extraction layer. In the present invention, the thickness of the light extraction layer is preferably 20 to 100nm, more preferably 30 to 80nm.
The invention has no special requirement on the preparation method of the electroluminescent device, and can be realized by adopting the conventional method in the field. The invention preferably adopts vacuum deposition, vacuum evaporation, spin coating, casting, LB method, ink-jet printing, laser printing or LITI method to prepare the electroluminescent device.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Under the protection of nitrogen gas, the mixture is0.01mol of raw material a-1 and 0.025mol of raw material b-1 are dissolved in Tetrahydrofuran (THF) to obtain a first mixed solution; to the first mixed solution was added 0.1mmol Pd (PPh 3 ) 4 15mL of K with a molar concentration of 3mol/L 2 CO 3 Carrying out a first reflux reaction for 8 hours under the protection of nitrogen in the aqueous solution; sampling a spot plate, cooling to 25 ℃ after confirming that the reaction is complete, filtering a reaction mixture through a diatomite pad, washing with chloroform, and purifying the obtained filtrate by silica gel column chromatography after evaporating the filtrate in vacuum to obtain a first intermediate, wherein a mixed solution of hexane and toluene used for the silica gel column chromatography purification is used as an eluent;
under the protection of nitrogen, 0.01mol of the first intermediate and 0.015mol of raw material d-1 are dissolved in 150mL of toluene to obtain a third mixed solution; adding 5X 10 to the third mixed solution -5 mol Pd 2 (dba) 3 ，5×10 -5 mol P(t-Bu) 3 The third reflux reaction was performed at 110 ℃ for 24h, and the reaction was observed by TLC until the reaction was complete. Naturally cooling to 25 ℃, filtering, rotationally steaming the filtrate obtained by filtering until no fraction exists, and passing through a neutral silica gel column to obtain the 1,2, 4-triazole compound with the structure shown in (5);
the first reflux reaction equation is:
the third reflux reaction equation is:
elemental analysis structure (C) 41 H 24 N 6 O 3 ) Theoretical value: c,75.92; h,3.73; n,12.96; test value: c,75.94; h,3.71; n,12.98.MS: theoretical 648.19 and measured 649.16.
Examples 2 to 11
1,2, 4-triazole compounds were prepared in the same manner as in example 1, except that table 1 was referred to.
Table 1 examples 1 to 11 raw materials and products for preparing 1,2, 4-triazole-based compounds
Example 12
Under the protection of nitrogen, 0.02mol of raw material a-1 and 0.025mol of raw material b-1 are dissolved in Tetrahydrofuran (THF) to obtain a first mixed solution; to the first mixed solution was added 0.15mmol Pd (PPh 3 ) 4 25mL of K with a molar concentration of 3mol/L 2 CO 3 Carrying out a first reflux reaction for 12h under the protection of nitrogen in the aqueous solution; sampling the spot plate, cooling to 25 ℃ after confirming the reaction is complete, filtering the reaction mixture through a diatomite pad, washing with chloroform, and purifying the obtained filtrate by silica gel column chromatography after evaporating the filtrate in vacuum to obtain a first intermediate, wherein the silica gel column chromatography is purified by using a mixed solution of hexane and toluene as an eluent;
under the protection of nitrogen, 0.02mol of the first intermediate and 0.02mol of the raw material b-1 are dissolved in Tetrahydrofuran (THF) to obtain a second mixed solution; to the second mixed solution was added 0.15mmol Pd (PPh 3 ) 4 25mL of K with a molar concentration of 3mol/L 2 CO 3 Carrying out a second reflux reaction for 16h under the protection of nitrogen; sampling the spot plate, cooling to 25 ℃ after confirming the reaction is complete, filtering the reaction mixture through a diatomite pad, washing with chloroform, and purifying the obtained filtrate by silica gel column chromatography after evaporating the filtrate in vacuum to obtain a second intermediate, wherein the silica gel column chromatography is purified by using a mixed solution of hexane and toluene as an eluent;
under the protection of nitrogen, 0.01mol of second intermediate and 0.015mol of raw material are introducedd-1 is dissolved in 150mL of toluene to obtain a third mixed solution; adding 5X 10 to the third mixed solution -5 mol Pd 2 (dba) 3 ，5×10 -5 mol P(t-Bu) 3 The third reflux reaction was performed at 110 ℃ for 24h, and the reaction was observed by TLC until the reaction was complete. Naturally cooling to 25 ℃, filtering, rotationally steaming the filtrate obtained by filtering until no fraction exists, and passing through a neutral silica gel column to obtain the 1,2, 4-triazole compound with the structure shown in (100);
the first reflux reaction equation is:
the second reflux reaction equation is:
the third reflux reaction equation is:
elemental analysis structure (C) 51 H 35 N 5 O) theoretical value: c,83.47; h,4.81; n,9.54; test value: c,83.46; h,4.86; n,9.53.MS: theoretical 733.28, found 734.27.
Examples 13 to 16
1,2, 4-triazole compounds were prepared in the same manner as in example 12, except that table 2 was referred to.
Table 2 raw materials and products for preparing 1,2, 4-triazole Compounds from examples 12 to 16
The values of the molecular weights in tables 1 and 2 were measured using LC-MS.
The compounds prepared in examples 1 to 16 were dissolved in a deuterated chloroform solvent and 1H-NMR thereof was measured using a 500MHz NMR apparatus, and the resultant nuclear magnetic data are shown in Table 3.
TABLE 3 Nuclear magnetic resonance data for the Compounds prepared in examples 1 to 16
Test case
An electroluminescent device was prepared as follows:
a) Taking transparent glass as a substrate layer 1, washing an anode layer 2 (Ag (100 nm)), firstly using isopropanol and deionized water to carry out ultrasonic cleaning for 10min, then using ultraviolet rays to irradiate for 10min, and exposing the anode layer to ozone for cleaning;
b) Evaporating HAT-CN with the thickness of 10nm on the anode layer 2 by a vacuum evaporation mode to form a hole injection layer 3;
c) HT-1 with a thickness of 140nm is evaporated on the hole injection layer 3 by a vacuum evaporation method to form a hole transport layer 4;
d) EB-1 having a thickness of 30nm was vapor deposited as an electron blocking layer 5 on the hole transport layer 4 by vacuum vapor deposition;
e) A luminescent layer 6 with the thickness of 40nm is evaporated on the empty electron blocking layer 5, GH-2 and GH-1 are used as main materials, GD-1 is used as doping materials, and the mass ratio of GH-2, GH-1 and GD-1 is 45:45:10;
f) On the luminescent layer 6, evaporating ET-1 and Liq with the mass ratio of 1:1 by a vacuum evaporation mode to serve as an electron transport layer 7, wherein the thickness of the electron transport layer 7 is 40nm;
g) Over the electron transport layer 7, liF having a thickness of 1nm was vacuum-evaporated as an electron injection layer 8;
h) On the electron injection layer 8, mg and Ag with the mass ratio of 1:9 are used as a cathode layer 9 by vacuum evaporation, and the thickness of the cathode layer 9 is 15 nm;
i) A light extraction layer material having a thickness of 70nm was deposited on the cathode layer 9 by vacuum deposition to obtain an electroluminescent layer 10An optical device; the light extraction layer material is 1,2, 4-triazole compound or Alq prepared in examples 1-16 3 ；
Wherein HAT-CN is
HT-1 is->
EB-1 is
GD-1 is->
ET-1 is->
GH-1 is
GH-2 is->
Liq is->
Alq 3 Is that
The structure of the electroluminescent device is shown in fig. 1, wherein 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking layer/electron transport layer, 8 is an electron injection layer, 9 is a cathode layer, and 10 is a light extraction layer;
1,2, 4-triazole compounds and Alq prepared by using examples 1 to 16 3 Electroluminescent devices were prepared as light extraction layer materials, with the differences noted in table 4.
Table 4 composition of electroluminescent device
At 10mA/cm using an IVL (Current-Voltage-Brightness) test system 2 The current efficiency of the prepared electroluminescent device was measured at the current density of (2), and the measurement results are shown in table 5.
Table 5 Properties of electroluminescent devices prepared
From the results of table 5, it can be seen that the 1,2, 4-triazole compound provided by the invention can effectively improve the light extraction efficiency of the OLED light-emitting device as the light extraction layer of the OLED light-emitting device. Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The 1,2, 4-triazole compound is characterized by having a structure shown in a formula I:
wherein L is 1 、L 2 、L 3 Independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene group containing one or moreA heteroatom substituted or unsubstituted 5-to 30-membered heteroarylene;
Ar 1 、Ar 2 、Ar 3 independently is a structure shown in any one of formulas 2-6, and Ar 1 、Ar 2 And Ar is a group 3 At least one of them is a group of the structure shown in formula 2:
wherein X is-O-, -S-or-NR-, R is C 1 ～C 10 An alkyl group of (a) a substituted or unsubstituted 6-to 30-membered aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group;
R 1 、R 2 、R 3 、R 4 independently hydrogen, deuterium, tritium, halogen, cyano, C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, and when R 1 、R 2 、R 3 、R 4 R when they are each a substituted or unsubstituted 6-to 30-membered aryl group or a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms 1 、R 2 、R 3 、R 4 Respectively connected with the parallel rings of the formulas 2, 3 and 4;
L 4 、L 5 independently a single bond, a substituted or unsubstituted 6-to 30-membered arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms;
R 5 、R 6 independently C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6 to 30 membered aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group containing one or more heteroatoms;
R 7 a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the heteroatoms in the heteroaryl and heteroarylene groups are independently oxygen, sulfur or nitrogen;
the substituents in the substituted aryl, substituted heteroaryl, substituted arylene and substituted heteroarylene are independently protium, deuterium, tritium, halogen, cyano and C 1 ～C 10 Alkyl, C of (2) 1 ～C 10 An alkoxy group, a substituted or unsubstituted 6 to 20 membered aryl group, or a substituted or unsubstituted 5 to 20 membered heteroaryl group containing one or more heteroatoms.
2. The 1,2, 4-triazole compound of claim 1 having a structure represented by any one of formulas i-1 to i-34:
wherein, represents a substitutable site.
3. The 1,2, 4-triazole compound of claim 1, wherein the 1,2, 4-triazole compound has a structure represented by formula i-35 or formula i-36:
4. the 1,2, 4-triazole compound of claim 1, wherein the 1,2, 4-triazole compound has a structure as shown in formulas i-37 to i-39:
5. the 1,2, 4-triazole compound of claim 1, wherein the 1,2, 4-triazole compound has a structure represented by formulas i-40 to i-41:
6. the 1,2, 4-triazole compound of claim 1, wherein L 2 Is a single bond, a substituted or unsubstituted 6-20 membered arylene, a substituted or unsubstituted 5-20 membered heteroarylene containing one or more heteroatoms;
the L is 1 、L 3 Independently is a substituted or unsubstituted 6-20 membered arylene, substituted or unsubstituted 5-20 membered heteroarylene containing one or more heteroatoms.
7. The 1,2, 4-triazole compound of claim 1 or 6, wherein L 1 、L 2 And L 3 Independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazole group, or a substituted or unsubstituted dibenzoylene groupA furyl group;
r is methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted biphenyl;
R 1 、R 2 、R 3 、R 4 independently hydrogen, protium, deuterium, tritium, halogen, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridinyl, or substituted or unsubstituted furanyl;
L 4 、L 5 independently is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazole group, or a substituted or unsubstituted dibenzofuranylene group;
R 5 、R 6 independently is methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted dibenzothiophenyl, or substituted or unsubstituted dibenzofuranyl;
R 7 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenyl groupSubstituted dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted dibenzothienyl or substituted or unsubstituted dibenzofuranyl;
the substituent of the substituent group is protium, deuterium, tritium, cyano, fluoro, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, naphthyridinyl, biphenyl, terphenyl, pyridyl, carbazolyl or dibenzofuranyl.
8. The 1,2, 4-triazole compound according to claim 7, wherein the 1,2, 4-triazole compound has a structure represented by any one of the following structural formulas:
9. the process for producing 1,2, 4-triazole compound according to any one of claims 1 to 8, comprising the steps of:
mixing a substance with a structure shown in a formula a, a substance with a structure shown in a formula b, tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a first organic solvent, and performing a first reflux reaction to obtain a first intermediate;
mixing the first intermediate, a substance with a structure shown in a formula c, tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a second organic solvent, and performing a second reflux reaction to obtain a second intermediate;
(HO) 2 B-L 3 -Ar 3
formula c;
mixing the second intermediate, a substance with a structure shown in a formula d, a third organic solvent, tris (dibenzylideneacetone) dipalladium and tris (tertiary butyl) phosphine for a third reflux reaction to obtain a 1,2, 4-triazole compound with a structure shown in a formula I;
(HO) 2 B-L 2 -Ar 2
formula d.
10. An electroluminescent device comprising a substrate, a first electrode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer/electron transport layer, an electron injection layer, a second electrode layer, and a light extraction layer which are sequentially stacked, wherein the light extraction layer is prepared from the 1,2, 4-triazole compound according to any one of claims 1 to 8 or the 1,2, 4-triazole compound prepared by the preparation method according to claim 9.
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