CN111423455A - Bithiophene fused heterocycle organic compound and application thereof - Google Patents
Bithiophene fused heterocycle organic compound and application thereof Download PDFInfo
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- CN111423455A CN111423455A CN202010243271.5A CN202010243271A CN111423455A CN 111423455 A CN111423455 A CN 111423455A CN 202010243271 A CN202010243271 A CN 202010243271A CN 111423455 A CN111423455 A CN 111423455A
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- -1 heterocycle organic compound Chemical class 0.000 title claims abstract description 31
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 32
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 41
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 17
- 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
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 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
- 239000000126 substance Substances 0.000 claims description 8
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001769 aryl amino group Chemical group 0.000 claims description 6
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 125000004306 triazinyl group Chemical group 0.000 claims description 6
- 125000005580 triphenylene group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 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
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 75
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000007787 solid Substances 0.000 description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 20
- 238000010992 reflux Methods 0.000 description 20
- 238000001704 evaporation Methods 0.000 description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 16
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SFUIGUOONHIVLG-UHFFFAOYSA-N (2-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1[N+]([O-])=O SFUIGUOONHIVLG-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- KPGPIQKEKAEAHM-UHFFFAOYSA-N 2-chloro-3-phenylquinoxaline Chemical compound ClC1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 KPGPIQKEKAEAHM-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 238000005516 engineering process 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
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RADLTTWFPYPHIV-UHFFFAOYSA-N (2-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1S RADLTTWFPYPHIV-UHFFFAOYSA-N 0.000 description 1
- NXYICUMSYKIABQ-UHFFFAOYSA-N 1-iodo-4-phenylbenzene Chemical group C1=CC(I)=CC=C1C1=CC=CC=C1 NXYICUMSYKIABQ-UHFFFAOYSA-N 0.000 description 1
- XEGAYWQRXAVWSD-UHFFFAOYSA-N 2-chloro-3-naphthalen-1-ylquinoxaline Chemical compound C1=CC=C2C(C3=NC4=CC=CC=C4N=C3Cl)=CC=CC2=C1 XEGAYWQRXAVWSD-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- ISMDILRWKSYCOD-GNKBHMEESA-N C(C1=CC=CC=C1)[C@@H]1NC(OCCCCCCCCCCCNC([C@@H](NC(C[C@@H]1O)=O)C(C)C)=O)=O Chemical compound C(C1=CC=CC=C1)[C@@H]1NC(OCCCCCCCCCCCNC([C@@H](NC(C[C@@H]1O)=O)C(C)C)=O)=O ISMDILRWKSYCOD-GNKBHMEESA-N 0.000 description 1
- 229940126639 Compound 33 Drugs 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
- 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
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ARCLXLACKDXCPM-UHFFFAOYSA-N benzoic acid phenylboronic acid Chemical compound C1(=CC=CC=C1)B(O)O.C(C1=CC=CC=C1)(=O)O ARCLXLACKDXCPM-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 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
- 239000003086 colorant Substances 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
- 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
- 238000000605 extraction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 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
- 150000002739 metals Chemical class 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
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 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
-
- 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
- C07D495/22—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 four or more hetero rings
-
- 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
- C07D495/12—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 three hetero rings
- C07D495/14—Ortho-condensed systems
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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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Abstract
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a bi-thiophene fused heterocyclic organic compound and application thereof. The organic compound has a parent structure of a bithiophene fused heterocycle, has high bond energy among atoms, has good thermal stability, is favorable for solid-state accumulation among molecules, and can effectively prolong the service life of the material when being used as a luminescent layer material. The compound is a large conjugated fused heterocyclic derivative, is applied in a light-emitting layer, has a proper energy level with an adjacent layer, is favorable for injecting holes and electrons, can effectively reduce the starting voltage, and can realize good luminous efficiency in a device at a higher exciton migration rate. 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 bi-thiophene fused heterocyclic organic compound and application thereof.
Background
Organic electroluminescent display (hereinafter referred to as O L ED) has a series of advantages of self-luminescence, low-voltage direct-current drive, full curing, wide viewing angle, light weight, simple composition and process, etc. compared with liquid crystal display, the organic electroluminescent display does not need backlight source, and has large viewing angle, low power, response speed up to 1000 times of that of the liquid crystal display, and manufacturing cost lower than that of the liquid crystal display with the same resolution.
With the continuous advance of the O L ED technology in the two fields of illumination and display, people pay more attention to the research on efficient organic materials affecting the performance of O L ED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of the device structure and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Compared with inorganic luminescent materials, organic electroluminescent materials have many advantages, such as good processability, flexible display and large-area display, and can be formed on any substrate by evaporation or spin coating, and there is a large space for selecting materials by changing the structure of molecules, adjusting the optical properties, electrical properties, stability, etc. in the most common structure of an O L ED device, organic materials, such as hole injection materials, hole transport materials, electron transport materials, and luminescent materials (dyes or doped guest materials) and corresponding host materials of various colors, are usually included.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bithiophene fused heterocyclic organic compound and application thereof.
The technical scheme for solving the technical problems is as follows: a bi-thiophene fused heterocyclic organic compound has the following structural formula:
wherein R is1-R8Each independently is hydrogen, C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30Any one of heteroaryl;
X1、X2each independently is a chemical bond, O, S, CR9R10Or NR11,Y1、Y2Each independently is a chemical bond, O, S, CR9R10Or NR11’And X1、X2、Y1、Y2At least one of which is N;
R9、R10each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30Any one of heteroaryl; r11Is substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30A heteroaryl group.
Further, R1-R11、R11’Wherein the substituents of the selected groups are each independently hydrogen, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Further, R1-R8Each independently is hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
Further, R9、R10Each independently is methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
Further, R11、R11’Each 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, R1-R8In (b), any two adjacent groups are linked to form a ring by a chemical bond.
Further, adjacent R9、R10Is connected into a ring through chemical bonds.
Further, the structural formula of the above organic compound is preferably 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 organic light-emitting layer, and the host material of the organic light-emitting layer comprises at least one organic compound.
The invention has the beneficial effects that:
the organic compound has a parent structure of a bithiophene fused heterocycle, has high bond energy among atoms, has good thermal stability, is favorable for solid-state accumulation among molecules, and can effectively prolong the service life of the material when being used as a luminescent layer material. The compound is a large conjugated fused heterocyclic derivative, is applied in a light-emitting layer, has a proper energy level with an adjacent layer, is favorable for injecting holes and electrons, can effectively reduce the starting voltage, and can realize good luminous efficiency in a device at a higher exciton migration rate. 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) dissolving 100mmol of bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 200mmol of NBS in batches, stirring at normal temperature, reacting for 8h, adding water into the reaction solution, separating out solids, and filtering to obtain a white solid M1;
(2) 100mmol of M1, 220mmol of o-nitrobenzeneboronic acid and (1%) Pd (PPh) are added into a reaction bottle3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M2;
(3) adding 100mmol of intermediate M2 into 1000M L o-dichlorobenzene solution in a reaction bottle, adding 300mmol of triphenylphosphine, heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M3;
(4) 100mmol of intermediate M3, 220mmol of 4-iodobiphenyl and Pd are added into a reaction bottle2(dba)30.9g (0.785mmol, 0.5 percent), toluene 1500m L and sodium tert-butoxide 40g (300mmol) are reacted at 100 ℃ for 5 hours, the reaction is stopped after the reaction is finished, the reactant is cooled to room temperature, water is added, the reaction solution is extracted by ethyl acetate, the concentration and the organic phase column chromatography are carried out, and the obtained solid is recrystallized and purified by toluene to obtain A1.
1H NMR(400MHz,Chloroform)8.00(s,1H),7.91(d,J＝8.0Hz,3H),7.50(d,J＝12.0Hz,4H),7.41-7.11(m,5H)。
Example 2
Synthesis of Compound A7, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) dissolving 100mmol bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 100mmol NBS in batches at 0 ℃, stirring at normal temperature, reacting for 8h, adding water into the reaction solution to precipitate a solid, and filtering to obtain a white solid M1;
(2) the reaction flask was charged with M1(100mmol), o-nitrobenzeneboronic acid (110mmol) and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M2;
(3) adding 100mmol of intermediate M2 into 1000M L o-dichlorobenzene solution, adding (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M3;
(4) adding M3(100mmol), 2-chloro-3-phenylquinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000M L DMF into a reaction bottle, reacting at 120 ℃ for 12h, 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 yellow powder M4;
(5) dissolving 100mmol of M4 in 500M L dichloromethane, adding NBS (N-bromosuccinimide) in batches at 0 ℃, stirring at normal temperature for 8 hours, reacting, adding water into the reaction solution, separating out solids, and filtering to obtain yellow solid M5;
(6) to a reaction flask, M5(100mmol), methyl orthoformate phenylboronic acid (110mmol), and Pd (1%) in PPh3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M6;
(7) in ice bath, adding M6(100mmol) into a reaction bottle, dissolving in 500M L THF, dropwise adding methyl magnesium bromide (220mmol), controlling the temperature, naturally heating to room temperature after dropwise adding, reacting for 8h, adding water into the reaction solution, extracting with ethyl acetate, and concentrating the organic phase to obtain an intermediate M7;
(8) adding M7(100mmol) and glacial acetic acid 1500M L into a reaction bottle, reacting at 100 ℃ for 12h, stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water and ethyl acetate for extraction, concentrating, performing organic phase column chromatography, and recrystallizing the obtained solid in toluene to purify to obtain A7.
1H NMR(CDCl3,400MHz)8.40-8.23(m,3H),7.95-7.80(m,3H),7.72(d,J＝12.0Hz,4H),7.61–7.44(m,4H),7.44(t,J＝6.4Hz,1H),7.40(t,J＝12.0Hz,2H),1.69(s,6H)。
Example 3
Synthesis of Compound A13, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) dissolving 100mmol bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 100mmol NBS in batches at 0 ℃, stirring at normal temperature, reacting for 8h, adding water into the reaction solution to precipitate a solid, and filtering to obtain a white solid M1;
(2) the reaction flask was charged with M1(100mmol), o-nitrobenzeneboronic acid (110mmol) and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M2;
(3) adding 100mmol of intermediate M2 into 1000M L o-dichlorobenzene solution, adding (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M3;
(4) adding M3(100mmol), 2-chloro-3-phenylquinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000M L DMF into a reaction bottle, reacting at 120 ℃ for 12h, 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 yellow powder M4;
(5) dissolving 100mmol of M4 in 500M L dichloromethane, adding NBS (N-bromosuccinimide) in batches at 0 ℃, stirring at normal temperature for 8 hours, reacting, adding water into the reaction solution, separating out solids, and filtering to obtain yellow solid M5;
(6) to a reaction flask, M5(100mmol), o-nitrobenzeneboronic acid (110mmol) and (1%) Pd (PPh) were added3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M6;
(7) adding M6(100mmol) into a reaction bottle, dissolving in 1000M L o-dichlorobenzene solution, adding (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, removing solvent by evaporation, performing silica gel column chromatography, and separating to obtain intermediate M7;
(8) adding M7(100mmol), iodobenzene (110mmol), (1%) Pd (dba), (1%) S-Phos, sodium tert-butoxide (40 g (300mmol) and xylene (800M L) into a reaction bottle, heating to reflux, reacting for 8h, extracting the reaction liquid with ethyl acetate, and concentrating the organic phase to obtain yellow solid A13.
1H NMR(CDCl3,400MHz)8.25-8.13(m,2H),8.01(d,J＝10.0Hz,4H),7.80(d,J＝7.6Hz,3H),7.72–7.57(m,7H),7.51(dd,J＝9.2,6.0Hz,4H),7.11(s,1H),6.92(s,1H)。
Example 4
Synthesis of Compound A25, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) dissolving 100mmol bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 100mmol NBS in batches at 0 ℃, stirring at normal temperature, reacting for 8h, adding water into the reaction solution to precipitate a solid, and filtering to obtain a white solid M1;
(2) the reaction flask was charged with M1(100mmol), o-nitrobenzeneboronic acid (110mmol) and (1%) Pd (PPh)3)440g (300mmol) of sodium carbonate, 800m of toluene L, 200m of ethanol L and 200m of water L are heated to reflux and react for 8 hours, and the reaction solution is reacted with ethyl acetateExtracting, and concentrating the organic phase to obtain yellow solid M2;
(3) adding 100mmol of intermediate M2 into 1000M L o-dichlorobenzene solution, adding (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M3;
(4) adding M3(100mmol), 2-chloro-3-naphthylquinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000M L DMF into a reaction bottle, reacting at 120 ℃ for 12h, 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 yellow powder M4;
(5) dissolving 100mmol of M4 in 500M L dichloromethane, adding NBS (N-bromosuccinimide) in batches at 0 ℃, stirring at normal temperature for 8 hours, reacting, adding water into the reaction solution, separating out solids, and filtering to obtain yellow solid M5;
(6) to a reaction flask, M5(100mmol), o-mercaptophenylboronic acid (110mmol), and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M6;
(7) adding M6(100mmol) into a reaction bottle, dissolving in 1000M L o-dichlorobenzene solution, adding triphenylphosphine (300mmol), heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain A25
1H NMR(CDCl3,400MHz)8.15-8.07(m,2H),8.01(d,J＝10.0Hz,3H),7.80(d,J＝7.6Hz,3H),7.72–7.57(m,5H),7.51(dd,J＝9.2,6.0Hz,2H),7.11-7.02(m,4H)。
Example 5
Synthesis of Compound A27, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) dissolving 100mmol bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 100mmol NBS in batches at 0 ℃, stirring at normal temperature, reacting for 8h, adding water into the reaction solution to precipitate a solid, and filtering to obtain a white solid M1;
(2) the reaction flask was charged with M1(100mmol), o-nitrobenzeneboronic acid (110mmol) and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M2;
(3) adding 100mmol of intermediate M2 into 1000M L o-dichlorobenzene solution, adding (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M3;
(4) adding M3(100mmol), 2- (5-bromo- [1,1' -diphenyl ] -3-yl) -4-phenylquinazoline (100mmol), potassium carbonate 40g (300mmol) and 1000M L DMF in a reaction bottle, reacting at 120 ℃ for 12h, 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 yellow powder M4;
(5) dissolving 100mmol of M4 in 500M L dichloromethane, adding NBS (N-bromosuccinimide) in batches at 0 ℃, stirring at normal temperature for 8 hours, reacting, adding water into the reaction solution, separating out solids, and filtering to obtain yellow solid M5;
(6) to a reaction flask, M5(100mmol), o-phenolic benzoate phenylboronic acid (110mmol), and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M6;
(7) in ice bath, adding M6(100mmol) into a reaction bottle, dissolving in 500M L THF, dropwise adding (220mmol) methyl magnesium bromide, controlling the temperature, naturally heating to room temperature after dropwise adding, reacting for 8h, adding water into the reaction solution, extracting with ethyl acetate, and concentrating the organic phase to obtain an intermediate M7;
(8) adding M7(100mmol) and glacial acetic acid 1500M L into a reaction bottle, reacting at 100 ℃ for 12h, stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, extracting with ethyl acetate, concentrating, carrying out organic phase column chromatography, and recrystallizing the obtained solid in toluene to purify to obtain A27.
1H NMR(CDCl3,400MHz)：8.29(d,J＝12.0Hz,3H),8.13(s,1H),7.99(d,J＝10.4Hz,2H),7.89–7.70(m,3H),7.65(s,2H),7.57–7.45(m,4H),7.40(q,J＝10.0Hz,4H),7.28(s,1H),7.23(d,J＝10.0Hz,4H),7.11(s,1H),6.92(s,1H),2.28(s,3H).
Example 6
Synthesis of compound 33, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) dissolving 100mmol bithiophene in 500M L dichloromethane, adding into a reaction bottle, adding 100mmol NBS in batches at 0 ℃, stirring at normal temperature, reacting for 8h, adding water into the reaction solution to precipitate a solid, and filtering to obtain a white solid M1;
(2) adding M1(100mmol), 2-chloroaniline (110mmol), (1%) Pd (dba), (1%) S-Phos, sodium tert-butoxide (40 g (300mmol) and xylene 800M L into a reaction bottle, heating to reflux, reacting for 8h, adding water after the reaction is finished, extracting the reaction liquid with ethyl acetate, and concentrating an organic phase to obtain a yellow solid M2;
(3) 100mmol of intermediate M2, (3%) Pd (OAC)2Heating tricyclohexylphosphine, (1%) 40g (300mmol) of sodium carbonate and DMAC800M L to reflux, reacting for 12h, adding water, extracting the reaction solution with ethyl acetate, concentrating the organic phase, and performing column chromatography separation to obtain a yellow solid M3;
(4) adding M3(100mmol), 2-chloro-3-phenylquinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000M L DMF into a reaction bottle, reacting at 120 ℃ for 12h, 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 yellow powder M4;
(5) dissolving 100mmol of M4 in 500M L dichloromethane, adding NBS (N-bromosuccinimide) in batches at 0 ℃, stirring at normal temperature for 8 hours, reacting, adding water into the reaction solution, separating out solids, and filtering to obtain yellow solid M5;
(6) to a reaction flask, M5(100mmol), methyl orthoformate phenylboronic acid (110mmol), and Pd (1%) in PPh3)4Heating 40g (300mmol) of sodium carbonate, 800M of toluene L, 200M of ethanol L and 200M of water L to reflux, reacting for 8 hours, extracting reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M6;
(7) in ice bath, adding M6(100mmol) into a reaction bottle, dissolving in 500M L THF, dropwise adding (220mmol) methyl magnesium bromide, controlling the temperature, naturally heating to room temperature after dropwise adding, reacting for 8h, adding water into the reaction solution, extracting with ethyl acetate, and concentrating the organic phase to obtain an intermediate M7;
(8) adding M7(100mmol) and glacial acetic acid 1500M L into a reaction bottle, reacting at 100 ℃ for 12h, stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, extracting with ethyl acetate, concentrating, carrying out organic phase column chromatography, and recrystallizing the obtained solid in toluene to purify to obtain A33.
1H NMR(CDCl3,400MHz)8.55-8.40(m,2H),7.80(s,1H),7.72(d,J＝12.0Hz,3H),7.61–7.44(m,4H),7.44(d,J＝8.0Hz,2H),7.40(t,J＝12.0Hz,3H),7.16-7.11(m,4H),1.69(s,6H)。
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 O L ED includes first and second electrodes on a substrate, and an organic layer between the electrodes, which may 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, an electron injection layer, and the substrate may be formed using a conventional substrate used in an organic light emitting display in the related art, for example, glass, polymer materials, glass with TFT components, polymer materials, and the like.
The anode material may be as in the prior artKnown Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO)2) 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, but not limited to, magnesium silver mixture, L iF/Al, ITO and other metals, metal mixture, oxide and other materials and structures.
The O L ED device may also include a hole injection layer, a hole transport layer between the light emitting layer and the anode, which may be, but not limited to, compounds shown below as HT-1 through HT-31, 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 between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, one or a combination of L iQ, L iF, NaCl, CsF, &lTtT translation = L "&gTt L &/T &gTt i2O,Cs2CO3,BaO,Na,Li,Ca。
The effects of the compounds obtained in examples 1 to 6 of the present invention and the control GPH-16 as host materials for light emitting layers in devices are described in detail by performance tests below.
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, the main material is A1, A7, A13, A25, A27, A33 and GPH-16 respectively 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 to be 3%, and the total thickness of the evaporation film is 30 nm;
(5) an electron transport layer of the device is vacuum evaporated on the light emitting layer, and the material ET-42 is selected, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
(6) l iF with the thickness of 0.5nm is vacuum-evaporated on the electron transport layer (ET L) 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, the ratio of brightness to current density is the current efficiency, and the service life of L T95 is tested by using a brightness 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 a main 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 a main 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 (10)
1. A bi-thiophene fused heterocyclic organic compound is characterized in that the structural formula is as follows:
wherein R is1-R8Each independently is hydrogen, C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30Any one of heteroaryl;
X1、X2each independently is a chemical bond, O, S, CR9R10Or NR11,Y1、Y2Each independently is a chemical bond, O, S, CR9R10Or NR11’And X1、X2、Y1、Y2At least one of which is N;
R9、R10each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C3-C30Any one of heteroaryl; r11、R11’Each independently is substituted or unsubstituted C6-C30Aryl or substituted or unsubstitutedC of (A)3-C30A heteroaryl group.
2. An organic compound according to claim 1, wherein R is1-R11、R11’Wherein the substituents of the selected groups are each independently hydrogen, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
3. An organic compound according to claim 1, wherein R is1-R8Each independently is hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
4. An organic compound according to claim 1, wherein R is9、R10Each independently is methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
5. An organic compound according to claim 1, wherein R is11、R11’Each 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 is1-R8In (b), any two adjacent groups are linked to form a ring by a chemical bond.
7. An organic compound according to claim 1, wherein adjacent R's are9、R10Is connected into a ring through chemical bonds.
8. An organic compound according to claim 1, having the formula:
9. use of an organic compound according to any one of claims 1 to 8 in an organic electroluminescent device.
10. 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 organic light-emitting layer, the host material of which comprises at least one organic compound according to any one of claims 1 to 7.
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