CN111004213B - Organic electroluminescent compound and application thereof - Google Patents
Organic electroluminescent compound and application thereof Download PDFInfo
- Publication number
- CN111004213B CN111004213B CN201911367916.XA CN201911367916A CN111004213B CN 111004213 B CN111004213 B CN 111004213B CN 201911367916 A CN201911367916 A CN 201911367916A CN 111004213 B CN111004213 B CN 111004213B
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- China
- Prior art keywords
- organic electroluminescent
- electroluminescent compound
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- substituted
- electron transport
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 claims description 40
- -1 benzofluorenyl group Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229940126062 Compound A Drugs 0.000 claims description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000001624 naphthyl group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000001725 pyrenyl group Chemical group 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 20
- 238000001704 evaporation Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 12
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- 235000010290 biphenyl Nutrition 0.000 description 10
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 10
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- 238000002347 injection Methods 0.000 description 9
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
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- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 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 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 125000005561 phenanthryl group Chemical group 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
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- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000005343 heterocyclic alkyl group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 3
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- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- UKSZBOKPHAQOMP-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 UKSZBOKPHAQOMP-UHFFFAOYSA-N 0.000 description 1
- OHCPVLJEAHBMEG-UHFFFAOYSA-N 1-acetylpiperidine-4-carbonyl chloride Chemical compound CC(=O)N1CCC(C(Cl)=O)CC1 OHCPVLJEAHBMEG-UHFFFAOYSA-N 0.000 description 1
- WFCLWJHOKCQYOQ-UHFFFAOYSA-N 1-acetylpiperidine-4-carboxylic acid Chemical compound CC(=O)N1CCC(C(O)=O)CC1 WFCLWJHOKCQYOQ-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QIOZCMIWAVEQPN-UHFFFAOYSA-N [10-(4-phenylphenyl)anthracen-9-yl]boronic acid Chemical compound C12=CC=CC=C2C(B(O)O)=C2C=CC=CC2=C1C(C=C1)=CC=C1C1=CC=CC=C1 QIOZCMIWAVEQPN-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
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- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
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- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 125000004957 naphthylene group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- CXLGNJCMPWUZKM-UHFFFAOYSA-N oxane-4-carbaldehyde Chemical compound O=CC1CCOCC1 CXLGNJCMPWUZKM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005560 phenanthrenylene group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000005548 pyrenylene group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—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
- C07D403/04—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 directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D421/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings
- C07D421/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
The invention provides an organic electroluminescent compound and application thereof, wherein the organic electroluminescent compound has a structure shown in a formula I, and is a novel micromolecular compound containing benzimidazole groups and heterocycloalkyl. The service life LT95 of the OLED device containing the organic electroluminescent compound is remarkably prolonged at 90 ℃, the application requirement of the OLED device at high temperature can be fully met, and the organic electroluminescent compound has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an organic electroluminescent compound and application thereof.
Background
An Organic Light Emitting Display (OLED) is a novel flat panel Display, and compared with a Liquid Crystal Display (LCD), the OLED has the advantages of being thin, Light, wide in viewing angle, capable of actively Emitting Light, continuously adjustable in Light Emitting color, low in cost, fast in response speed, low in energy consumption, low in driving voltage, wide in working temperature range, simple in production process, high in Light Emitting efficiency, capable of flexibly displaying and the like, and has received great attention from the industry and the scientific community, and meanwhile, the development of the OLED has promoted the research of people on Organic electroluminescent materials. Compared with inorganic luminescent materials, organic electroluminescent materials have the following advantages: the organic material has good processing performance, and can form a film on any substrate by an evaporation or spin coating method; the diversity of the organic molecular structure can adjust the thermal stability, mechanical property, luminescence and conductivity of the organic material by the method of molecular structure design and modification, so that the material has great space for improvement.
The generation of organic electroluminescence is based on the recombination of the carriers (i.e. electrons and holes) transported in the organic semiconductor material, however, the conductivity of the organic material is poor, there is no continuous energy band in the organic semiconductor, and the transport of carriers is often described by hopping theory. In order to make the organic electroluminescent device breakthrough in application, the difficulties of poor charge injection and transport capabilities of organic materials must be overcome. Scientists can adjust the device structure to increase the number of organic material layers of the device and make different organic layers as different device layers, for example, some functional materials can promote the injection of electrons from the cathode, some functional materials can promote the injection of holes from the anode, some materials can promote the transport of charges, and some materials can play the role of blocking the transport of electrons or holes. Therefore, the organic electroluminescent device with good efficiency and long service life is generally the result of optimized matching of the device structure and various organic materials, which provides great opportunity and challenge for chemists to design and develop functional materials with various structures.
The electron transport layer is an important component in the organic electroluminescent device, has better electron accepting capability, and can effectively transfer electrons under certain forward bias. The electron transport materials disclosed at present mainly comprise 8-hydroxyquinoline aluminum compounds, imidazole compounds, nitrogen-containing six-membered heterocyclic compounds, oxadiazole compounds, triazole compounds, perfluorinated compounds and the like. For example, CN105754589A, CN104072405A, CN1784388, CN107935936A, etc. disclose an electron transport material and an organic electroluminescent device comprising the same, but the performance thereof still cannot meet the requirements of OLED devices in various application scenarios.
The mainstream technology of the preparation process of the organic electroluminescent device at present is an evaporation method, namely, each functional material is plated on a substrate to form a film in a vacuum thermal evaporation mode, and in the method, the long-time high-temperature thermal evaporation process has high requirements on the thermal stability of the material, and the evaporation rate needs to be stably controlled for a long time, so that the uniformity of the material distribution on the substrate is kept; and the utilization rate of the raw materials of the evaporation process is low and is generally below 20 percent. In addition, the OLED device is widely applied to various fields such as display, illumination and the like, wherein the high-temperature environment is not lacked, for example, in a vehicle instrument, the temperature in the vehicle can reach 60 ℃ or even approach 90 ℃, so that higher requirements are provided for the high-temperature service life of the OLED device and the material thereof. The service life of the OLED material disclosed in the prior art at high temperature is not ideal.
Therefore, it is a research focus in the art to develop a wider variety of high-performance OLED materials to improve the high-temperature stability of the OLED device and to prolong the service life of the OLED device at high temperature.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organic electroluminescent compound and application thereof, wherein the organic electroluminescent compound obviously improves the high-temperature stability of the organic electroluminescent compound as an electron transport material through the special design of a molecular structure and a functional group, so that the driving voltage of an OLED device is reduced, and the high-temperature service life of the OLED device is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an organic electroluminescent compound having a structure represented by formula I:
wherein X is N-H, O, S or Se.
Ring A is a substituted or unsubstituted C6-C40 aryl group.
And the ring B is substituted or unsubstituted C2-C10 heterocycloalkyl.
Ar is substituted or unsubstituted C6-C50 aryl.
When the ring A and the ring B, Ar have substituent groups, the substituent groups are selected from at least one of C1-C20 straight-chain or branched alkyl, C1-C20 alkoxy or C6-C30 aromatic hydrocarbon.
In the present invention, the substitution includes mono-, di-or poly-substitution.
In the present invention, the C6 to C40 aryl group may be C6, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C37, or C39, and the like, and exemplarily includes, but is not limited to, phenyl, biphenyl, naphthyl, anthryl, pyrenyl, phenanthryl, fluorenyl, or benzofluorenyl, and the like.
The C2-C10 heterocycloalkyl group may be a C2, C3, C4, C5, C6, C7, C9 or C10 heterocycloalkyl group, and the heteroatom is X.
The C6 to C50 aryl group may be an aryl group of C6, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C38, C40, C43, C45, C47, or C49, etc., and exemplarily includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a fluorenyl group, a benzophenanthryl group, or a benzofluorenyl group, etc.
The C1-C20 linear or branched alkyl group may be a C2, C4, C6, C8, C10, C13, C15, C17, or C19 linear or branched alkyl group, and exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or pentyl, and the like.
The C6 to C30 aromatic hydrocarbon group may be an aromatic hydrocarbon group of C6, C8, C10, C13, C15, C18, C20, C23, C25, C28, or C29, etc., and exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, biphenyl, naphthyl, or anthryl, etc.
And the ring B is substituted or unsubstituted C2-C10 heterocycloalkyl, wherein the heteroatom is X, namely the heterocycloalkyl containing O, S, Se or N.
The organic electroluminescent compound provided by the invention has a structure shown in a formula I, and is a novel micromolecular organic matter containing a benzimidazole group, wherein a condensed structure of a ring A and an imidazolyl group, a heterocyclic alkyl group of a ring B and an Ar aryl group are matched with each other, so that the organic electroluminescent compound is endowed with good photoelectric properties, the condensed structure of the ring A and the imidazolyl group is a typical structure with electron transmission performance, and the structure of the heterocyclic alkyl group of the ring B can improve the film forming performance of molecules, so that the acting force between the molecules after film forming is increased; meanwhile, by selecting Ar, the HOMO and the LOMO of the whole molecular structure can be adjusted according to the needs, and particularly, the HOMO of the molecule is finely adjusted under the condition that the LUMO of the molecule is kept relatively stable, so that when the organic electroluminescent compound is used for preparing an OLED device, the energy level of the organic electroluminescent compound is better matched with the energy level of an adjacent material, and the organic electroluminescent compound is more suitable for preparing the OLED device with high performance.
Preferably, the ring B is selected from any one of the following groups, or any one of the following groups substituted with a substituent group:
wherein the dotted line represents the attachment site of the group.
The substituent is at least one selected from C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight-chain or branched alkyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkoxy or C6-C20 (such as C7, C9, C10, C12, C14, C15, C17 or C19) aryl. Wherein, the C1-C10 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, etc., the C1-C10 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, etc., and the C6-C20 aryl group exemplarily includes but is not limited to phenyl, naphthyl, anthryl, biphenyl, etc.
Preferably, the organic electroluminescent compound has a structure shown in formula I-1 or formula I-2:
wherein, X1Selected from O, S or Se.
Ring a, ring B, Ar each independently have the same limitations as described above.
Preferably, Ar has a structure as shown in formula II:
Ar1-Ar2----
formula II.
Wherein the dotted line represents the attachment site of the group.
Ar1Is a substituted or unsubstituted aryl group of C6-C30 (e.g., C8, C10, C13, C15, C18, C20, C23, C25, C28, C29, etc.) illustratively including, but not limited to, phenyl, biphenyl, naphthyl, anthryl, pyrenyl, phenanthryl, fluorenyl, triphenyleneAnd benzofluorenyl groups.
Ar2And substituted or unsubstituted arylene groups of C6 to C20 (e.g., C7, C9, C10, C12, C14, C15, C17, C19, etc.), illustratively including but not limited to phenylene, biphenylene, naphthylene, anthrylene, pyrenylene, phenanthrenylene, fluorenylene, benzophenanthrylene, or benzofluorenylene, and the like.
When the above groups have a substituent, the substituent is selected from at least one of C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight-chain or branched-chain alkyl groups, C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) alkoxy groups, or C6 to C20 (e.g., C7, C9, C10, C12, C14, C15, C17, or C19) aromatic hydrocarbon groups. Wherein, the C1-C10 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, etc., the C1-C10 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, etc., and the C6-C20 aromatic hydrocarbon group exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, naphthyl, anthryl, biphenyl, etc.
Preferably, Ar is1Selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group.
The substituent is at least one selected from C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight-chain or branched alkyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkoxy or C6-C20 (such as C7, C9, C10, C12, C14, C15, C17 or C19) aromatic hydrocarbon. Wherein, the C1-C10 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, etc., the C1-C10 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, etc., and the C6-C20 aromatic hydrocarbon group exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, naphthyl, anthryl, biphenyl, etc.
Preferably, Ar is2Selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group.
The substituent is at least one selected from C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight-chain or branched alkyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkoxy or C6-C20 (such as C7, C9, C10, C12, C14, C15, C17 or C19) aromatic hydrocarbon. Wherein, the C1-C10 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, etc., the C1-C10 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, etc., and the C6-C20 aromatic hydrocarbon group exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, naphthyl, anthryl, biphenyl, etc.
Preferably, the ring a is a substituted or unsubstituted C6 to C30 (e.g., C7, C9, C10, C13, C15, C18, C20, C23, C25, C28, or C29, etc.) aryl group, illustratively including but not limited to phenyl, biphenyl, naphthyl, anthryl, pyrenyl, phenanthryl, fluorenyl, benzophenanthryl, or benzofluorenyl group, etc.
When the above groups have a substituent, the substituent is selected from at least one of C1 to C20 (e.g., C2, C4, C6, C8, C10, C13, C15, C17, C19, etc.) straight-chain or branched alkyl groups, C1 to C20 (e.g., C2, C4, C6, C8, C10, C13, C15, C17, C19, etc.) alkoxy groups, or C6 to C30 (e.g., C8, C10, C13, C15, C18, C20, C23, C25, C28, C29, etc.) aromatic hydrocarbon groups. Wherein, the C1 to C20 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, nonyl, etc., the C1 to C20 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, butoxy, etc., and the C6 to C30 aromatic hydrocarbon group exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, naphthyl, anthryl, phenanthryl, biphenyl, etc.
Preferably, the ring a is selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted phenanthryl group, and a substituted or unsubstituted pyrenyl group.
When the above groups have a substituent, the substituent is selected from at least one of C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight-chain or branched-chain alkyl groups, C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) alkoxy groups, or C6 to C20 (e.g., C7, C9, C10, C12, C14, C15, C17, or C19) aromatic hydrocarbon groups. Wherein, the C1-C10 linear or branched alkyl group exemplarily includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, etc., the C1-C10 alkoxy group exemplarily includes but is not limited to methoxy, ethoxy, propoxy, etc., and the C6-C20 aromatic hydrocarbon group exemplarily includes but is not limited to phenyl, tolyl, dimethylphenyl, ethylphenyl, naphthyl, anthryl, biphenyl, etc.
Preferably, the organic electroluminescent compound is selected from any one of the following compounds:
the organic electroluminescent compound with the structure shown in the formula I-1 is prepared by the following synthetic route, and specifically comprises the following steps:
(a1)
(a2)
(a3)
(a4)
in steps (a1) to (a4), ring a is a substituted or unsubstituted C6 to C40 aryl group, ring B is a substituted or unsubstituted C2 to C10 heterocycloalkyl group, Ar is a substituted or unsubstituted C6 to C50 aryl group, and U is chlorine, bromine, or iodine.
The organic electroluminescent compound with the structure shown in the formula I-2 is prepared by the following synthetic route, and specifically comprises the following steps:
(b1)
(b2)
(b3)
in steps (B1) to (B3), ring A is a substituted or unsubstituted C6-C40 aryl group, ring B is a substituted or unsubstituted C2-C10 heterocycloalkyl group, Ar is a substituted or unsubstituted C6-C50 aryl group, U is chlorine, bromine, or iodine, and X is1O, S or Se.
In another aspect, the present invention provides an electron transport material comprising any one or a combination of at least two of the organic electroluminescent compounds as described above.
Preferably, the electron transport material comprises an organic electroluminescent compound a and an organic electroluminescent compound B; the organic electroluminescent compound A has a structure shown as a formula I-1; the organic electroluminescent compound B has a structure shown as a formula I-2.
Preferably, the mass ratio of the organic electroluminescent compound a to the organic electroluminescent compound B is (0.01 to 10):1, for example, 0.02:1, 0.04:1, 0.06:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 9.8:1, and the like, and further preferably (0.3 to 3): 1.
As a preferred technical scheme of the invention, the electron transport material comprises an organic electroluminescent compound A and an organic electroluminescent compound B, wherein the organic electroluminescent compound A is a compound containing N heterocyclic alkyl shown in formula I-1, and the organic electroluminescent compound B is a compound containing O, S or Se heterocyclic alkyl. The organic electroluminescent compound A and the organic electroluminescent compound B can form hydrogen bonds at a high temperature of more than 60 ℃, so that the stability of the organic electroluminescent compound A and the organic electroluminescent compound B as an electron transport material is remarkably improved, the driving voltage of an OLED device containing the electron transport material is reduced, and the high-temperature service life LT95 is prolonged to more than 150 h.
In another aspect, the present invention provides an OLED device comprising an electron transport layer comprising an electron transport material as described above.
In another aspect, the present invention provides an electronic device comprising an OLED device as described above.
Compared with the prior art, the invention has the following beneficial effects:
the organic electroluminescent compound provided by the invention is a novel organic micromolecular compound containing benzimidazole group and heterocycloalkyl, can be used as an electron transport material in an OLED device, and the organic electroluminescent compound A with the structure shown in the formula I-1 and the organic electroluminescent compound B with the structure shown in the formula I-2 can form intermolecular hydrogen bonds in an environment with the temperature of more than 60 ℃, so that the stability of the organic electroluminescent compound as the electron transport material is remarkably improved. The OLED device containing the electron transport material has good carrier transport capacity, can effectively reduce the drive voltage of the device, remarkably prolongs the high-temperature service life of the OLED device, prolongs the service life LT95 of the OLED device at 90 ℃ to more than 155h, even reaches 182h, and can fully meet the application requirement of the OLED device at high temperature.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides an organic electroluminescent compound, which has the following structure:
the preparation method comprises the following steps:
(1)
into a 2000mL three-necked flask, 300mL of toluene, 300mL of ethanol, and 100mL of water were added under nitrogen protection, 37.4g (0.1mol) of 9- (4-phenylphenyl) -anthracene-10-boronic acid, 15.7g (0.1mol) of p-chloronitrobenzene, 5.78g (0.005mol) of tetrakis (triphenylphosphine) palladium, and 27.6g (0.2mol) of potassium carbonate were added with stirring, and the mixture was slowly heated to reflux for 8 hours, cooled, separated with water, the organic layer was concentrated to dryness, and recrystallized with a mixed solvent of ethanol and toluene to obtain 39.6g in total of intermediate M1-1 as a yellowish solid with a yield of 87.8%.
Test M1-1 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 451.
(2)
adding 20g (0.044mol) of intermediate M1-1 into a 500mL autoclave, then adding 200mL of toluene, 80mL of ethanol and 5g of 5% Pd/C catalyst (dry weight), carrying out hydrogenation reaction after nitrogen replacement, controlling the hydrogen pressure at 0.5MPa and the temperature at 80 ℃, cooling after reaction for 10h, stopping the reaction, filtering the reaction solution after nitrogen replacement, concentrating the mother solution to dryness to obtain 18.05g of intermediate M1-2 totally, wherein the yield is 96.7%.
Test M1-2 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 421.
(3)
100mL of dry toluene were added to a 500mL three-necked flask under nitrogen, followed by 4.21g (0.01mol) of intermediate M1-2, 1.26g (0.008mol) of 2-chloronitrobenzene, 0.0575g (0.0001mol) of palladium bis (dibenzylidene acetone) (Pd) (dba)2And 1.15g (0.012mol) of sodium tert-butoxide, heating to reflux reaction for 6h, cooling, adding water for separating liquid, concentrating an organic layer to dryness, separating by silica gel column chromatography, and reacting with petroleum ether: eluting with a solvent at a ratio of dichloromethane to 5:1 (by volume) to obtain3.71g of intermediate M1-3 in total, yield 85.5%.
Test M1-3 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 542;
1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.25-8.18(m,5H)，7.88(s,1H)，7.76(m,2H)，7.69(m,1H)，7.61(m,1H)，7.55(m,2H)，7.52-7.40(m,8H)，7.35(m,2H)，7.26(s,4H)。
(4)
Adding 15g (0.0277mol) of intermediate M1-3 into a 500mL autoclave, then adding 200mL of toluene, 100mL of isopropanol and 3g of 5% Pd/C catalyst (dry weight), carrying out hydrogenation reaction after nitrogen replacement, controlling the hydrogen pressure at 0.5MPa and the temperature at 80 ℃, cooling after 10h of reaction, stopping the reaction, filtering the reaction solution after nitrogen replacement, concentrating the mother solution to dryness, recrystallizing the toluene and ethanol mixed solvent to obtain 11.8g of intermediate M1-4 and the yield of 83.18%.
Test M1-4 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 512.
(5)
to a 500mL three-necked flask, 17.1g (0.1mol) of 1-acetylpiperidine-4-carboxylic acid and 200mL of cyclohexane were added, 14.28g (0.12mol) of thionyl chloride was added with stirring, the temperature was slowly raised to 50 ℃ to react for 1 hour, the dry solvent cyclohexane and the remaining thionyl chloride were concentrated under reduced pressure to obtain a yellowish viscous substance, intermediate A1-5, i.e., 1-acetylpiperidine-4-carbonyl chloride (theoretical yield: 0.1mol), and then 200mL of dichloromethane was added to dissolve it to obtain an intermediate A1-5 solution which was not further separated, and this solution was directly subjected to the reaction of step (6).
(6)
Adding 400mL of dichloromethane into a 1000mL three-necked bottle under the protection of nitrogen, then adding 41g (0.08mol) of intermediate M1-4 and 9.5g (0.12mol) of pyridine, dropwise adding the intermediate A1-5 solution obtained in the step (5) at the temperature of 5-10 ℃, slowly heating to 35 ℃ after dropwise adding, reacting for 6 hours, cooling to 0 ℃, filtering to remove pyridine hydrochloride obtained in the reaction, concentrating the obtained mother liquor to dryness to obtain an intermediate A1-6, and directly performing the step (7) without separation.
(7)
A1000 mL three-necked flask was charged with 500mL of xylene and 15g of anhydrous p-toluenesulfonic acid, followed by the addition of intermediate A1-6 prepared in step (6) to give intermediate A1-7.
Test A1-7 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 647.
(8)
adding 6.48g (0.01mol) of intermediate A1-7, 200mL of tetrahydrofuran and 100mL of ethanol into a 500mL three-necked flask under the protection of nitrogen, slowly adding 5.6g (0.1mol) of potassium hydroxide under stirring, controlling the temperature to be 35 ℃, stirring for reaction for 24 hours, cooling, pouring a reaction solution into 1000mL of water, filtering to obtain a solid, drying the obtained solid at 50 ℃ and under 0.09MPa, performing column chromatography separation, and performing separation by using petroleum ether: dichloromethane: the target product a1 was obtained in a total amount of 3.1g with methanol (8.5: 1:0.5 by volume) and the yield was 51.17%.
Test a1 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 605;
1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl 3): δ 8.56(m,1H), 8.22(m,4H), 7.83-7.72(m,6H), 7.58-7.43(m,8H), 7.32-7.18(m,6H), 3.38(m,1H), 2.83(m,2H), 2.71(m,2H), 1.74(m,2H), 1.51(m,2H), 1.35(s, 1H).
Example 2
This example provides an organic electroluminescent compound, which has the following structure:
the preparation method comprises the following steps:
(1) intermediate M1-4 was obtained in the same manner as in steps (1) to (4) of example 1;
(5)
adding 5.13g (0.01mol) of intermediate M1-4, 1.14g (0.01mol) of tetrahydropyran-4-formaldehyde, 200mL of tetrahydrofuran and 5mL of glacial acetic acid into a 500mL three-necked flask under the protection of nitrogen, heating to 65 ℃, reacting for 16 hours, cooling, pouring a reaction solution into 1000mL of water, filtering to obtain a solid, drying the obtained solid at 50 ℃ and under the condition of-0.09 MPa, performing column chromatography separation, and performing separation by using petroleum ether: the solvent was eluted with 9:1 (vol.%) dichloromethane to give 4.9g total of the target product B1 in 80.8% yield.
Test B1 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 606;
1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.55(m,1H)，8.21(m,4H)，7.82-7.72(m,6H)，7.56-7.46(m,3H)，7.45-7.39(m,5H)，7.31-7.16(m,6H)，3.75(m,2H)，3.66(m,2H)，2.92(m,1H)，2.33(m,2H)，2.12(m,2H)。
Example 3
This example provides an organic electroluminescent compound, which has the following structure:
the preparation method differs from example 1 in that
In equimolar amounts
Replacement; subjecting the mixture obtained in the step (3)
In equimolar amounts
(purchased from Hebei Delong chemical Co., Ltd.); the target product A20 is obtained.
Test a20 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 629;
1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.56(m,1H)，8.25(m,5H)，8.07(m,3H)，8.05(m,1H)，7.84(m,1H)，7.81-7.72(m,4H)，7.71-7.65(m,2H)，7.64-7.54(m,3H)，7.43(m,4H)，7.39(m,1H)，2.90-2.65(m,5H)，1.82-1.68(m,2H)，1.57-1.46(m,2H)，1.45(m,1H)。
Example 4
This example provides an organic electroluminescent compound, which has the following structure:
the preparation method differs from example 2 in that in step (3)
In equimolar amounts
(purchased from Hebei Delong chemical Co., Ltd.); the target product B27 is obtained.
Test B27 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 772;
1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.27-8.18(m,7H)，8.12(d,1H)，8.07(d,1H)，7.82-7.73(m,6H)，7.60(m,1H)，7.55-7.39(m,8H)，7.31(m,1H)，7.27(s,4H)，3.80-3.58(m,4H)，2.90(m,1H)，2.37(m,2H)，2.11(m,2H)，1.72(s,6H)。
Example 5
The embodiment provides an organic electroluminescent compound, which has the following structure:
the preparation method differs from example 1 in that in step (5)
In equimolar amounts
(purchased from Hebei Delong chemical Co., Ltd.); the target product A2 is obtained.
Test a2 structure: the test value m/z was obtained by a mass spectrometer (Autoflex type III time-of-flight mass spectrometer MALDI-TOF-MS): 591 of;
1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.58(m,1H)，8.23(m,4H)，7.83-7.75(m,6H)，7.56-7.44(m,8H)，7.33-7.12(m,6H)，3.59(m,1H)，3.41-3.29(m,2H)，3.12-2.94(m,2H)，2.07(m,1H)，1.86(m,1H)，1.33(m,1H)。
Application example 1
This application example provides an OLED device, OLED device structure is: an ITO anode, a hole injection layer (HIL02, thickness 100nm), a hole transport layer (NPB, thickness 40nm), an organic light emitting layer (EM1, thickness 30nm), an electron transport layer (thickness 20nm), an electron injection layer (LiF, thickness 0.5nm), and an Al cathode (thickness 150 nm).
The preparation steps are as follows:
(1) carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent conductive layer (serving as an anode) in a cleaning agent, then washing the glass substrate in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol, baking the glass substrate in a clean environment until the water is completely removed, cleaning the glass substrate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cation beams to improve the surface property and improve the binding capacity with a hole injection layer;
(2) placing the glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode to form HIL02 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 100 nm;
(3) carrying out vacuum evaporation on NPB (N-propyl bromide) on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
(4) vacuum evaporating EM1 on the hole transport layer to serve as an organic light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm;
(5) the organic electroluminescent compound A1 provided in example 1 of the present invention was vacuum-evaporated on the organic light-emitting layer as the electron transport layer of the device, the evaporation rate was 0.1nm/s, and the total film thickness was 20 nm;
(6) LiF with the thickness of 0.5nm and Al with the thickness of 150nm are evaporated on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
Application example 2
The present application example differs from application example 1 in that a1 in step (5) is replaced with B1.
Application example 3
The present application example differs from application example 1 in that step (5) employs a mixture of two organic electroluminescent compounds as an electron transport layer, a1 and B1 are placed in different evaporation sources, respectively, so that the total evaporation rate of the two organic electroluminescent compounds is 0.1nm/s, the total film thickness of evaporation is 20nm, the mass ratio of a1 to B1 is 1:9, and the mass ratio of a1 to B1 is achieved by controlling the heating temperature of the evaporation sources.
Application example 4
The present application example differs from application example 3 in that the mass ratio of a1 to B1 in step (5) is 2: 8.
Application example 5
The present application example differs from application example 3 in that the mass ratio of a1 to B1 in step (5) is 3: 7.
Application example 6
The present application example differs from application example 3 in that the mass ratio of a1 and B1 in step (5) is 4: 6.
Application example 7
The present application example differs from application example 3 in that the mass ratio of a1 and B1 in step (5) is 5: 5.
Application example 8
The present application example differs from application example 3 in that the mass ratio of a1 and B1 in step (5) is 6: 4.
Application example 9
The present application example differs from application example 3 in that the mass ratio of a1 and B1 in step (5) is 7: 3.
Application example 10
The present application example differs from application example 3 in that the mass ratio of a1 and B1 in step (5) is 8: 2.
Application example 11
The present application example differs from application example 3 in that the mass ratio of a1 to B1 in step (5) is 9: 1.
Application example 12
The present application example differs from application example 1 in that step (5) employs a mixture of two organic electroluminescent compounds as an electron transport layer, and a2 and B26 were placed in different evaporation sources, respectively, so that the total evaporation rate of the two organic electroluminescent compounds was 0.1nm/s, the total film thickness was 20nm, and the mass ratio of a2 to B26 was 5: 5.
Application example 13
The present application example differs from application example 1 in that step (5) employs a mixture of two organic electroluminescent compounds as an electron transport layer, and A3 and B27 were placed in different evaporation sources, respectively, so that the total evaporation rate of the two organic electroluminescent compounds was 0.1nm/s, the total film thickness was 20nm, and the mass ratio of A3 to B27 was 5: 5.
Comparative example 1
This comparative example differs from application example 1 in that A1 in step (5) was replaced with ET-1.
Comparative example 2
This comparative example differs from application example 7 in that A1 in step (5) was replaced with C1.
Comparative example 3
This comparative example differs from application example 7 in that A1 in step (5) was replaced with C2.
Comparative example 4
This comparative example differs from application example 7 in that A1 in step (5) was replaced with C3.
Comparative example 5
This comparative example differs from application example 7 in that B1 in step (5) was replaced with C4.
And (3) performance testing:
first, sublimation experiment
(1) 2.0g of the organic electroluminescent compound A1, liter, provided in example 1 were takenThe temperature is 300 ℃ and the pressure is 5.0 multiplied by 10-4Pa, yield 1.60g of sublimed A1, and sublimation yield 80% by heating the black residue in the boat with a sublimator of 0.31 g.
(2) 2.0g of the organic electroluminescent compound B1 provided in example 2 was taken, the sublimation temperature was 300 ℃ and the pressure was 5.0X 10-4Pa, yield of sublimated B1 was 1.81g in total, and yield of 0.12 g of black residue remaining in the sublimation boat was 90.5%.
(3) A sublimation experiment was carried out after mixing 1.0g of the organic electroluminescent compound A1 and 1.0g of the organic electroluminescent compound B1 at a sublimation temperature of 300 ℃ and a pressure of 5.0X 10-4Pa, sublimation experiments were carried out under these conditions until no more product had sublimed, yielding a total of 0.3g of sublimed product, with a sublimation yield of 15%.
The sublimed product is a mixture of A1 and B1, wherein the mass percent of A1 is 38.1% and the mass percent of B1 is 61.8% by testing through high performance liquid chromatography (HPLC, Shimadzu LC-20A). The sublimation temperature is raised to 500 ℃ and the pressure is 5.0X 10-4Pa, no more product was sublimated, and 1.65 g of blackish residue remained in the sublimation boat. The above experimental results show that under high temperature conditions, the organic electroluminescent compound a1 and the organic electroluminescent compound B1 are changed to form intermolecular hydrogen bonds, resulting in a decrease in sublimed materials.
The sublimation experiment proves that the organic electroluminescent compounds A1 and B1 form hydrogen bonds after being mixed.
Secondly, to further verify that intermolecular hydrogen bonds are formed at high temperatures by a1 and B1, the following experiment was performed:
an organic electroluminescent compound A1 was deposited on a glass substrate to form a film, and the infrared absorption spectrum of the film was measured at 3310cm by an infrared spectrometer (ThermoFisher corporation, nicolet is50)-1The peak of absorption with secondary amine group appears. Respectively standing the film at 40 deg.C, 50 deg.C, 60 deg.C and 90 deg.C for 1 hr, and testing the infrared absorption spectrum of the film at 3310cm in the infrared absorption spectrum of the film at 60 deg.C-1The absorption peak is reduced at 3190cm-1New place of originAbsorption peak of (4); 3310cm in infrared absorption spectrum of the film after standing at 90 deg.C-1Almost disappeared at 3190cm-1The new absorption peak appeared to become larger, and the absorption peak was changed here because of the influence of the amino group association between molecules of A1.
Organic electroluminescent compounds A1 and B1 were mixed at a ratio of 1:1 and evaporated on a glass substrate to form a film, and the infrared absorption spectrum of the film was measured at 3310cm by an infrared spectrometer (ThermoFisher corporation, nicolet is50)-1The peak of absorption with secondary amine group appears. Respectively standing the film at 40 deg.C, 50 deg.C, 60 deg.C and 90 deg.C for 1 hr, and testing the infrared absorption spectrum of the film at 3310cm in the infrared absorption spectrum of the film at 60 deg.C-1The absorption peak at the position is reduced and is 3190cm-1At a distance of 3220cm-1New absorption peak appears; 3310cm in infrared absorption spectrum of the film after standing at 90 deg.C-1Is equal to 3190cm-1Almost disappeared at 3220cm-1There appears a new absorption peak, here 3220cm-1The new absorption peak is the absorption peak of intermolecular hydrogen bond formed by A1 and B1, which proves that the organic electroluminescent compounds A1 and B1 provided by the invention form hydrogen bond at 60 ℃.
Performance test of OLED device
The brightness, the driving voltage, the current density and the LT95 at 90 ℃ of the OLED devices provided in the application examples 1 to 13 and the comparative examples 1 to 5 are tested by using an OLED-1000 multichannel accelerated aging life and photochromic performance analysis system produced in Hangzhou distance, wherein the LT95 refers to the time required for keeping the current density unchanged and the brightness reduced to 95% of the original brightness, and when testing the LT95 at 90 ℃, the tested device is placed on a clamp with a heating function, heated to 90 ℃ and kept at the temperature unchanged to test the time required for the brightness to be reduced to 95% of the original brightness. The specific test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, compared with the OLED device using the electron transport material ET-1 in the prior art (comparative example 1), the organic electroluminescent compound provided by the invention as the electron transport material of the OLED device can reduce the driving voltage of the OLED device and improve the service life of the device at high temperature. When the electron transport layer of the OLED device is the combination of the organic electroluminescent compound A with the structure shown in the formula I-1 and the organic electroluminescent compound B with the structure shown in the formula I-2, the organic electroluminescent compound A and the organic electroluminescent compound B can form hydrogen bonds at 60 ℃, the high-temperature stability of the OLED device is remarkably improved, the high-temperature service life LT95(90 ℃) of the OLED device is prolonged to 155-182 h, and the application requirement of the OLED device at high temperature can be fully met.
If the organic electroluminescent compound with the structure shown in formula I provided by the invention is not used as the electron transport material in the OLED device, an alkyl group is connected to the heteroatom of the ring B (comparative example 2), the ring B is a cycloalkyl group without the heteroatom (comparative example 3) or an aryl group (comparative example 4), or the ring B is replaced by an alkylalkoxy group (comparative example 5), and the electron transport material is not the combination of the organic electroluminescent compound A with the structure shown in formula I-1 and the organic electroluminescent compound B with the structure shown in formula I-2, the electron transport material cannot form a hydrogen bond at 60 ℃, so that the high-temperature stability of the OLED device is low, the high-temperature service life LT95(90 ℃) is only less than 15h, and the application requirement of the OLED device at high temperature cannot be met.
The applicant states that the present invention is illustrated by the above examples of the organic electroluminescent compounds of the present invention and their applications, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (9)
1. An organic electroluminescent compound, wherein the organic electroluminescent compound has a structure represented by formula I:
wherein X is N-H, O or S;
ring a is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group;
when the ring A has a substituent, the substituent is selected from at least one of C1-C20 straight-chain or branched-chain alkyl, C1-C20 alkoxy or C6-C30 aromatic hydrocarbon;
the ring B is selected from any one of the following groups, or any one of the following groups substituted by substituent groups:
wherein the dotted line represents the attachment site of the group;
the substituent is selected from at least one of C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy or C6-C20 aryl;
ar has a structure shown in formula II:
Ar1-Ar2----
formula II;
ar is1Selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
the substituent is selected from at least one of C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy or C6-C20 aromatic hydrocarbon;
ar is2Selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group;
the substituent is at least one of C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy or C6-C20 aromatic hydrocarbon.
2. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound has a structure represented by formula I-1 or formula I-2:
wherein, X1Selected from O or S;
ring a, ring B, Ar each independently have the same limitations as claim 1.
3. The organic electroluminescent compound according to claim 1 or 2, wherein the organic electroluminescent compound is selected from any one of the following compounds:
4. an electron transport material comprising any one or a combination of at least two of the organic electroluminescent compounds as claimed in any one of claims 1 to 3.
5. The electron transport material of claim 4, wherein the electron transport material comprises organic electroluminescent compound A and organic electroluminescent compound B; the organic electroluminescent compound A has a structure shown as a formula I-1; the organic electroluminescent compound B has a structure shown as a formula I-2;
wherein, X1Selected from O or S;
ring a, ring B, Ar each independently have the same limitations as claim 1.
6. The electron transport material according to claim 5, wherein the mass ratio of the organic electroluminescent compound A to the organic electroluminescent compound B is (0.01-10): 1.
7. The electron transport material according to claim 6, wherein the mass ratio of the organic electroluminescent compound A to the organic electroluminescent compound B is (0.3-3): 1.
8. An OLED device comprising an electron transport layer, wherein the electron transport layer comprises the electron transport material of any of claims 4 to 7.
9. An electronic device, characterized in that it comprises an OLED device according to claim 8.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002028839A1 (en) * | 2000-10-06 | 2002-04-11 | Neurogen Corporation | Benzimidazole and indole derivatives as crf receptor modulators |
| CN108409721A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and organic light emitting diode device |
| CN108440396A (en) * | 2018-03-23 | 2018-08-24 | 吉林奥来德光电材料股份有限公司 | A kind of luminous organic material and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002028839A1 (en) * | 2000-10-06 | 2002-04-11 | Neurogen Corporation | Benzimidazole and indole derivatives as crf receptor modulators |
| CN108409721A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and organic light emitting diode device |
| CN108440396A (en) * | 2018-03-23 | 2018-08-24 | 吉林奥来德光电材料股份有限公司 | A kind of luminous organic material and its preparation method and application |
Non-Patent Citations (11)
| Title |
|---|
| RN 1154232-47-9;CAS;《STN REGISTRY》;20090609 * |
| RN 1154232-54-8;CAS;《STN REGISTRY》;20090609 * |
| RN 1156771-35-5;CAS;《STN REGISTRY》;20090614 * |
| RN 1484243-96-0;CAS;《STN REGISTRY》;20131201 * |
| RN 1491984-04-3;CAS;《STN REGISTRY》;20131210 * |
| RN 1494652-62-8;CAS;《STN REGISTRY》;20131213 * |
| RN 1497458-79-3;CAS;《STN REGISTRY》;20131217 * |
| RN 1507747-18-3;CAS;《STN REGISTRY》;20131231 * |
| RN 1524223-77-5;CAS;《STN REGISTRY》;20140119 * |
| RN 1974920-22-3;CAS;《STN REGISTRY》;20160818 * |
| Ruthenium-catalyzed rearrangements of azobenzenes.II. The preparation of 1-phenylbenzimidazoles from azobenzene derivatives and primary alcohols catalyzed by ruthenium complexes;Alwyn Spencer;《Journal of Organometallic Chemistry》;19851231;第295卷(第1期);79-89 * |
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