CN111377943A - Quinary heterocyclic organic compound and application thereof - Google Patents
Quinary heterocyclic organic compound and application thereof Download PDFInfo
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- CN111377943A CN111377943A CN202010243245.2A CN202010243245A CN111377943A CN 111377943 A CN111377943 A CN 111377943A CN 202010243245 A CN202010243245 A CN 202010243245A CN 111377943 A CN111377943 A CN 111377943A
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- -1 heterocyclic organic compound Chemical class 0.000 title claims abstract description 26
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 43
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 125000005561 phenanthryl group Chemical group 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 9
- 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 8
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 8
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 8
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims description 8
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 8
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 8
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- 125000004306 triazinyl group Chemical group 0.000 claims description 8
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 7
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000005580 triphenylene group Chemical group 0.000 claims description 6
- 125000001769 aryl amino group Chemical group 0.000 claims description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000005264 aryl amine group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 32
- 150000001875 compounds Chemical class 0.000 abstract description 11
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 239000007787 solid Substances 0.000 description 33
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 239000000843 powder Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000012544 monitoring process Methods 0.000 description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 13
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- JNGKNTZYAKKNLQ-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1h-triazine Chemical compound N=1N(Cl)NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 JNGKNTZYAKKNLQ-UHFFFAOYSA-N 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 101000766357 Ruditapes philippinarum Big defensin Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- IYTUCLYDZGDBCM-UHFFFAOYSA-N (6-phenylpyridin-2-yl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=CC=CC=2)=N1 IYTUCLYDZGDBCM-UHFFFAOYSA-N 0.000 description 1
- QNGVEVOZKYHNGL-UHFFFAOYSA-N 2-chloro-4,6-diphenylpyrimidine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 QNGVEVOZKYHNGL-UHFFFAOYSA-N 0.000 description 1
- OBHKONRNYCDRKM-UHFFFAOYSA-N 4-chloro-2-phenylquinazoline Chemical compound N=1C2=CC=CC=C2C(Cl)=NC=1C1=CC=CC=C1 OBHKONRNYCDRKM-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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- 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
- C07D403/02—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 two hetero rings
- C07D403/10—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 two hetero rings linked by a carbon chain containing aromatic rings
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a pentabasic heterocyclic organic compound and application thereof. The organic compound has a parent structure of five-membered heterocycle, has the characteristic of good planar accumulation of molecules, has good thermal stability, and can effectively prolong the service life of the material when used as an electron transport layer material. The derivative of the bithiophene is applied to an electron transport layer, has a proper energy level with an adjacent layer, is favorable for injecting electrons, can effectively reduce the starting voltage, has a high electron transfer rate, and can realize good luminous efficiency in a device. The compound has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability and shows long service life in a device. The preparation process of the derivative is simple and easy to implement, the raw materials are easy to obtain, and the preparation method is suitable for mass production and amplification.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a pentabasic heterocyclic organic compound and application thereof.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by an electric current and an electric field under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical property, the electrical property, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a pentabasic heterocyclic organic compound and application thereof.
The technical scheme for solving the technical problems is as follows: a five-membered heterocyclic organic compound has the following structural formula:
wherein Ar is1、Ar2Each independently is substituted or unsubstituted C3-C30A heteroaromatic ring;
R1、R2each independently hydrogen, deuterium, substituted or unsubstituted C6-C30Aromatic ring or substituted or unsubstituted C3-C30A heteroaromatic ring;
L1、L2each independently a bond, substituted or unsubstituted C6-C30Aromatic ring or substituted or unsubstituted C3-C30A heteroaromatic ring;
x, Y are each independently O, S or CR3R4；
R3、R4Each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30A heteroaryl group.
Further, Ar1、Ar2、R1-R4、L1、L2In (1), substitution of selected groupsEach independently being hydrogen, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Further, Ar1、Ar2Each independently is a substituted or unsubstituted pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, or aza-dibenzothienyl group.
Further, R1、R2Each independently is hydrogen, deuterium, a substituted or unsubstituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, triphenylene group, fluorenyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, quinoxalinyl group, cinnolinyl group, naphthyridinyl group, triazinyl group, pyridopyrazinyl group, furyl group, benzofuryl group, dibenzofuryl group, aza-dibenzofuryl group, thienyl group, benzothienyl group, dibenzothienyl group, aza-dibenzothienyl group, phenanthryl group, 9-dimethylfluorenyl group, spirofluorenyl group, arylamino group, or carbazolyl group.
Further, L1、L2Each independently is a substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazole group.
Further, R3、R4Each independently being methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinylPyridyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
Further, the structural formula of the above organic compound is as follows:
the second object of the present invention is to provide the use of the above organic compounds in organic electroluminescent devices.
An organic electroluminescent device comprises a substrate, an anode layer, an organic layer at least comprising a light-emitting layer, and a cathode layer sequentially formed on the substrate; the organic layer comprises an electron transport layer comprising at least one organic compound as described above.
The invention has the beneficial effects that:
the organic compound has a parent structure of five-membered heterocycle, is represented by a parent structure of bithiophene, has the characteristic of good plane accumulation of molecules, has good thermal stability, and can effectively prolong the service life of the material when used as an electron transport layer material. The derivative of the bithiophene is applied to an electron transport layer, has a proper energy level with an adjacent layer, is favorable for injecting electrons, can effectively reduce the starting voltage, has a high electron transfer rate, and can realize good luminous efficiency in a device. The compound has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability and shows long service life in a device. The preparation process of the derivative is simple and easy to implement, the raw materials are easy to obtain, and the preparation method is suitable for mass production and amplification.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Synthesis of Compound A1, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding bithiophene (100mmol, 1.0eq) and 800mL of dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (200mmol, 2.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) a reaction flask was charged with 100mmol of intermediate M1, (220mmol) pinacol diboron, Pd (dppf) Cl2(1%), potassium acetate (300mmol) and 800mL of DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) to a reaction flask, intermediate M2(100 mmol), (200mmol) 2-chloro-4, 6-diphenyltriazine, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a white powder a 1.
1H NMR(400MHz,Chloroform)δ9.22(s,2H),8.36(m,8H),7.50(m,12H)。
Example 2
Synthesis of Compound A6, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding bithiophene (100mmol, 1.0eq) and 800mL of dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) the reaction flask was charged with (100mmol) intermediate M1, (100mmol) 2-phenyl- (4-phenylboronic acid) -benzimidazole, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) adding M2(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M3;
(4) to a reaction flask, intermediate M3(100 mmol), pinacol diboron (120mmol), Pd (dppf) Cl2(1%), potassium acetate (300mmol) and 800mL of DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M4;
(5) to a reaction flask, intermediate M4 (100mmol), (100mmol) 2-chloro-4, 6-diphenyltriazine, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a white powder a 6.
1H NMR(CDCl3,400MHz)δ9.15(s,1H),8.69(s,1H),8.56-8.36(m,5H),7.94–7.75(m,6H),7.52(d,J＝12.0Hz,4H),7.28-7.10(m,8H)。
Example 3
Synthesis of Compound A14, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding bithiophene (100mmol, 1.0eq) and 800mL of dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) the reaction flask was charged with (100mmol) intermediate M1, (100mmol) 6-phenyl- (2-pyridineboronic acid), Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) adding M2(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M3;
(4) to a reaction flask, intermediate M3(100 mmol), pinacol diboron (120mmol), Pd (dppf) Cl2(1%), potassium acetate (300mmol) and 800mL of DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M4;
(5) the intermediate M4 (100mmol), 2-chloro-4, 6-diphenylpyrimidine (100mmol) and Pd (PPh) were added to a reaction flask3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature,water was added, filtered and washed with water, and the resulting solid was purified by recrystallization from toluene to give a white powder a 6.
1H NMR(CDCl3,400MHz)：8.85(s,1H),8.78(s,1H),8.33(s,1H),7.94-7.65(m,4H),7.63–7.56(m,6H),7.52(d,J＝10.0Hz,4H),7.27(d,J＝8.0Hz,4H)。
Example 4
Synthesis of Compound A21, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding bithiophene (100mmol, 1.0eq) and 800mL of dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (200mmol, 2.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) a reaction flask was charged with 100mmol of intermediate M1, (220mmol) pinacol diboron, Pd (dppf) Cl2(1%), potassium acetate (300mmol) and 800mLDMF, and reacting at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) to a reaction flask, intermediate M2(100 mmol), (200mmol) 2-chloro-4, 6-diphenyltriazine, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M3;
(4) adding M3(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M4;
(5) to a reaction flask, intermediate M4 (100mmol), (110mmol) phenylboronic acid, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a white powder a 21.
1H NMR(CDCl3,400MHz)δ9.23(s,1H),8.36(m,8H),7.49(d,J＝6.0Hz,6H),7.39(m,7H),7.33(m,4H)。
Example 5
Synthesis of Compound A25, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding bithiophene (100mmol, 1.0eq) and 800mL of dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) the reaction flask was charged with (100mmol) intermediate M1, (100mmol) 2-phenyl- (4-phenylboronic acid) -benzimidazole, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) adding M2(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M3;
(4) to a reaction flask, intermediate M3(100 mmol), pinacol diboron (120mmol), Pd (dppf) Cl2(1%) VinegarPotassium (300mmol) and 800mL DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M4;
(5) to a reaction flask, intermediate M4 (100mmol), (100mmol) 2-chloro-4, 6-diphenyltriazine, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give M5 as a white powder.
(6) Adding M5(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M6;
(7) the reaction flask is added with (100mmol) intermediate M6, (100mmol) pyridine-2-boric acid, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M7;
(8) adding M7(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M8;
(9) the reaction flask is added with (100mmol) intermediate M8, (100mmol) phenylboronic acid and Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a white powder a 25.
1H NMR(CDCl3,400MHz)：8.56-8.32(m,2H),8.16-7.96(m,4H),7.80(d,J＝12.0Hz,2H),7.62-7.52(m,6H),7.50(dd,J＝12.0,10.0Hz,4H),7.38(d,J＝8.0Hz,4H),7.31(dd,J＝12.0,7.6Hz,4H),7.28-7.13(m,6H).
Example 6
Synthesis of Compound A32, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) adding benzofuran (100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M1;
(2) to a reaction flask, intermediate M1 (100mmol), pinacol diboron (120mmol), Pd (dppf) Cl2(1%), potassium acetate (300mmol) and 800mL of DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M2;
(3) adding 100mmol of intermediate M2, (100mmol) of 2-phenyl-4-chloroquinazoline and Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M3;
(3) adding M3(100mmol, 1.0eq) and 800mL dichloromethane into a reaction bottle, and stirring to dissolve the mixture to be clear; controlling the temperature to be less than 0 ℃, adding NBS (100mmol, 1.0eq) in batches, naturally heating to room temperature for 1h after adding, and monitoring the reaction completion by TLC; adding 1000mL of pure water, stirring for 30min, performing suction filtration, and drying to obtain a white solid M4;
(4) a reaction flask was charged with 100mmol of intermediate M4, (120mmol) of pinacol diboron, Pd (dp)pf)Cl2(1%), potassium acetate (300mmol) and 800mL of DMF at 120 ℃ for 12 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid in toluene to obtain white powder M5;
(5) to a reaction flask, intermediate M5(100 mmol), (100mmol) 2-chloro-4, 6-diphenyltriazine, Pd (PPh)3)4(1%), potassium carbonate 40g (300mmol), 800mL DMF and 200mL water, at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a white powder a 32.
1H NMR(CDCl3,400MHz)：8.36(d,J＝8.0Hz,2H),8.25(s,2H),8.13(s,2H),7.79(s,2H),7.57–7.55(m,6H),7.55–7.45(m,5H),7.30(s,2H).
The other compounds of the present invention can be synthesized by selecting raw materials with suitable structures according to the above-mentioned ideas of examples 1-6, and the synthesis process is not repeated here.
Device application example
The OLED includes first and second electrodes on a substrate, and an organic layer between the electrodes. The organic layer may in turn be divided into a plurality of regions. For example, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. The substrate is a conventional substrate used in an organic light emitting display in the related art, for example, glass, polymer materials, glass and polymer materials with TFT components, and the like.
The anode material may be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of these materials.
The cathode material can be selected from materials and structures such as, but not limited to, magnesium silver mixture, metal such as LiF/Al, ITO, etc., metal mixture, oxide, etc.
The OLED device can also comprise a hole injection layer and a hole transport layer which are positioned between the light-emitting layer and the anode, and the layers can be but are not limited to compounds shown in HT-1 to HT-31 below; or any combination thereof.
The device light emitting layer may comprise a host material and a light emitting dye, wherein the host material includes, but is not limited to, one or more combinations of conventional materials as shown in GPH1-GPH80 below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li2O,Cs2CO3,BaO,Na,Li,Ca。
The effect of the compounds obtained in examples 1 to 6 according to the invention and the control ET-42 as electron transport layer material in devices is explained in detail below by means of performance tests.
The preparation processes of the organic electroluminescent devices described in application examples 1 to 6 and comparative example 1 of the present invention were as follows:
(1) ultrasonically treating the glass plate coated with the ITO transparent conducting layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent, baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10-5Pa, vacuum evaporating HT-11 on the anode layer film to form a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
(3) evaporating HT-5 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
(4) a luminescent layer of the device is vacuum evaporated on the hole transport layer, the luminescent layer comprises a main material and a dye material, GPH-16 is selected as the main material by a multi-source co-evaporation method, the evaporation rate of the main material is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is set according to the proportion of 3%, and the total evaporation film thickness is 30 nm;
(5) vacuum evaporating an electron transport layer of the device on the luminescent layer, respectively selecting materials A1, A6, A14, A21, A25, A32 and ET-42, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
(6) LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the organic electroluminescent devices prepared in application examples 1 to 6 and comparative example 1 were measured for driving voltage, current efficiency and lifetime at the same luminance using a digital source meter and a luminance meter, and specifically, the luminance of the organic electroluminescent device reached 5000cd/m, as measured by increasing the voltage at a rate of 0.1V/sec2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 5000cd/m2The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance2Time in hours, the results are shown in table 1 below.
TABLE 1
As can be seen from the data in Table 1, the novel organic material prepared by the invention is used as an electron transport layer material of an organic electroluminescent device, can effectively reduce the rise-fall voltage, improve the current efficiency and prolong the service life of the device, and is an electron transport layer material with good performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A five-membered heterocyclic organic compound is characterized in that the structural formula is as follows:
wherein Ar is1、Ar2Each independently is substituted or unsubstituted C3-C30A heteroaromatic ring;
R1、R2each independently hydrogen, deuterium, substituted or unsubstituted C6-C30Aromatic ring or substituted or unsubstituted C3-C30A heteroaromatic ring;
L1、L2each independently a bond, substituted or unsubstituted C6-C30Aromatic ring or substituted or unsubstituted C3-C30A heteroaromatic ring;
x, Y are each independently O, S or CR3R4；
R3、R4Each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30A heteroaryl group.
2. The organic compound of claim 1, wherein Ar is Ar1、Ar2、R1-R4、L1、L2Wherein the substituents of the selected groups are each independently hydrogen, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
3. The organic compound of claim 1, wherein Ar is Ar1、Ar2Each independently is a substituted or unsubstituted pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl,Cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl or aza-dibenzothienyl.
4. An organic compound according to claim 1, wherein R is1、R2Each independently is hydrogen, deuterium, a substituted or unsubstituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, triphenylene group, fluorenyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, quinoxalinyl group, cinnolinyl group, naphthyridinyl group, triazinyl group, pyridopyrazinyl group, furyl group, benzofuryl group, dibenzofuryl group, aza-dibenzofuryl group, thienyl group, benzothienyl group, dibenzothienyl group, aza-dibenzothienyl group, phenanthryl group, 9-dimethylfluorenyl group, spirofluorenyl group, arylamino group, or carbazolyl group.
5. The organic compound of claim 1, wherein L is1、L2Each independently is a substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazole group.
6. An organic compound according to claim 1, wherein R is3、R4Each independently being methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinylA quinazoline group, a quinoxalinyl group, a cinnolinyl group, a naphthyridinyl group, a triazinyl group, a pyridopyrazinyl group, a furyl group, a benzofuryl group, a dibenzofuryl group, an aza-dibenzofuryl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an aza-dibenzothienyl group, a phenanthryl group, a 9, 9-dimethylfluorenyl group, a spirofluorenyl group, an arylamine group, or a carbazolyl group.
7. An organic compound according to claim 1, having the formula:
8. use of an organic compound according to any one of claims 1 to 7 in an organic electroluminescent device.
9. An organic electroluminescent device comprises a substrate, an anode layer, an organic layer at least comprising a light-emitting layer, and a cathode layer sequentially formed on the substrate; characterized in that the organic layer comprises an electron transport layer comprising at least one organic compound according to any one of claims 1 to 7.
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