CN110872261A - Organic semiconductor material substituted by oxadiazole containing spirofluorene, preparation method and OLED device - Google Patents
Organic semiconductor material substituted by oxadiazole containing spirofluorene, preparation method and OLED device Download PDFInfo
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- CN110872261A CN110872261A CN201811002698.5A CN201811002698A CN110872261A CN 110872261 A CN110872261 A CN 110872261A CN 201811002698 A CN201811002698 A CN 201811002698A CN 110872261 A CN110872261 A CN 110872261A
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- Prior art keywords
- organic semiconductor
- semiconductor material
- substituted
- formula
- suzuki reaction
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000004065 semiconductor Substances 0.000 title claims abstract description 46
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- MASXXNUEJVMYML-UHFFFAOYSA-N 2,2',7,7'-tetrabromo-9,9'-spirobi[fluorene] Chemical compound C12=CC(Br)=CC=C2C2=CC=C(Br)C=C2C11C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 MASXXNUEJVMYML-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- -1 1,3, 4-oxadiazole boric acid Chemical compound 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZRABUTWSVKKMAF-UHFFFAOYSA-N (5-phenyl-1,3,4-oxadiazol-2-yl)boronic acid Chemical compound O1C(B(O)O)=NN=C1C1=CC=CC=C1 ZRABUTWSVKKMAF-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 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 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ANYCDYKKVZQRMR-UHFFFAOYSA-N lithium;quinoline Chemical compound [Li].N1=CC=CC2=CC=CC=C21 ANYCDYKKVZQRMR-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
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- 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
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- 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
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- 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
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
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- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- 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
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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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
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Abstract
The invention provides an organic semiconductor material substituted by oxadiazole containing spirofluorene, a preparation method and an OLED device; the organic semiconductor material containing the spirofluorene oxadiazole substituent has high charge transfer capacity and high glass transition temperature, can prevent the crystallization of the material in the device manufacturing process, can be used as an electronic transmission material in an OLED device, can enable the current efficiency of the OLED device to reach more than 60Cd/A, and has long service Life (LT)95) Can reach more than 160h, has more excellent performance and higher application value compared with the phenanthroline and the compounds disclosed in the prior art.
Description
Technical Field
The invention belongs to the field of semiconductor materials, relates to an organic semiconductor material containing spirofluorene, and particularly relates to an organic semiconductor material substituted by oxadiazole containing spirofluorene, a preparation method and an OLED device.
Background
An Organic Light-Emitting Diode (OLED) is also called an Organic electroluminescent display or an Organic Light-Emitting semiconductor. The OLED display technology has the advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, extremely high reaction speed and the like. However, the price of the high-end display screen is more expensive than that of the liquid crystal television.
The advent and development of OLEDs has led to the rapid development of organic photovoltaic materials and devices. At present, the luminous efficiency and stability of the OLED have met the requirements of medium and small-sized displays, and are widely applied to instruments and high-end smart phones, and large-sized OLED televisions have already entered the market. In a period of time in the future, the OLED large-size technology will be continuously improved, and meanwhile, OLED lighting products will gradually enter the daily life of people.
In order to further achieve excellent performance of the organic light emitting diode, materials constituting the organic material layer, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and the like, should be stable and have excellent efficiency. When the organic light emitting diode is manufactured by vacuum deposition, the operation or storage at a high temperature condition may cause a change in emitted light, a decrease in light emitting efficiency, an increase in driving voltage, and a reduction in lifetime. In order to prevent these problems, it is necessary to develop a novel electron transport material having a high glass transition temperature and capable of reducing a driving voltage.
CN103304557A discloses an organic semiconductor material containing spirofluorene, whose structural formula is as follows:
in the semiconductor material provided by the method, the phenylbenzimidazole is an electron-deficient group and is used as an electron transport group; oxadiazole is also an electron-deficient group, and the existence of the group enables the organic semiconductor material containing spirofluorene to have better electron transport performance. The special rigid structure of the spirofluorene enables the organic semiconductor material containing the spirofluorene to have strong thermal stability. However, the Lifetime (LT) of the compounds of this structure as electron transport layers in OLED devices95) Shorter and less efficient.
CN107325084A discloses a spirofluorene-xanthene compound and a light emitting device thereof, which have the following structures:
wherein, Y1、Y2Each independently represents hydrogen, an electron withdrawing group or an electron donating group; x1、X2In which at least one substituent is of the formula
Wherein M represents-S-, -P-, -SO2-、-S(＝S)-、-S(＝S)(＝S)-、-PO-、-PO2-、-P(＝S)-、-P(＝S)(＝S)-、-C(＝O)-；N1、N2、N3、N4Each independently represents a carbon atom or a nitrogen atom; raSelected from hydrogen, halogen, C1～30Alkyl, hydroxy substituted C1～30Alkyl or C6～48An alkylaryl group; j. k and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 1 to 4. However, the maximum current efficiency of the compound provided by the method is only less than 50%, and the efficiency is low.
CN106632219A discloses a spirofluorene derivative, the structural formula of which is as follows:
wherein R is substituted or unsubstituted C1～C60Alkyl, substituted or unsubstituted C6～C60Aryl, substituted or unsubstituted C5～C60Condensed ring group of, substituted or unsubstituted C5～C60The heterocyclic group of (1). However, the current efficiency of such spirofluorene derivatives is also low, and needs to be further improved.
Therefore, how to develop a novel compound and improve the performance of the OLED device has important significance for expanding the application of the OLED device to higher-end fields.
The present invention relates to a compound for organic light emission, which has high charge transfer capability and high glass transition temperature, and can prevent crystallization of a material during device fabrication.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a spirofluorene-containing oxadiazole substituted organic semiconductor material, a preparation method and an OLED device, so that the current efficiency of the OLED device is improved, and LT (linear transformation) is adopted95The service life is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an oxadiazole-substituted organic semiconductor material containing spirofluorene, wherein the structure of the organic semiconductor material is shown in formula I:
wherein, L is any one of aromatic ring, aromatic heterocyclic ring, substituted aromatic ring or substituted aromatic heterocyclic ring, and n is an integer of 0-3 (for example, 0, 1, 2 or 3);
r is independently selected from hydrogen, deuterium, substituted C6～C60(may be, for example, C)6、C12、C18、C24、C30、C36、C42、C48、C54、C60Etc.) aromatic ring, C6～C60(may be, for example, C)6、C12、C18、C24、C30、C36、C42、C48、C54、C60Etc.) aromatic ring, substituted C5～C60(may be, for example, C)5、C6、C12、C18、C24、C30、C36、C42、C48、C54、C60Etc.) aromatic heterocyclic ring, C5～C60(may be, for example, C)5、C6、C12、C18、C24、C30、C36、C42、C48、C54、C60Etc.) aromatic heterocyclic ring, C1～C50(may be, for example, C)1、C4、C8、C18、C30、C40、C42、C48、C50Etc.) alkyl or substituted C1～C50(may be, for example, C)1、C4、C8、C18、C30、C40、C42、C48、C50Etc.) or a combination of at least two of the same.
More specifically, the above aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a spirofluorene ring, or the like; the aromatic heterocyclic ring may be furan ring, thiophene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, benzofuran ring, benzimidazole ring, quinoline ring, isoquinoline ring, etc. or combinations thereof.
The alkyl group can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like or combinations thereof.
The substituted group may be a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or the like.
The oxadiazole substituted organic semiconductor material containing spirofluorene has high charge transfer capacity and high glass transition temperature, can prevent crystallization of the material in the device manufacturing process, can be used as an electronic transmission material in an OLED device, can enable the current efficiency of the OLED device to reach more than 60Cd/A, and has long service Life (LT)95) Can reach over 160h, and has more excellent performance compared with the phenanthroline and the compounds disclosed in the prior art.
In the invention, the existence of the L group can improve the Tg point of the material, and is beneficial to improving the thermal stability of the material.
Preferably, the organic semiconductor material is any one of the following structures:
preferably, the organic semiconductor material has a structure of
In the invention, the materials with the two structures are preferably selected and applied to OLED devices, and the performance is more excellent.
In a second aspect the present invention provides a process for the preparation of an organic semiconducting material as described in the first aspect, the process comprising the steps of: 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene and a compound of a formula II are subjected to Suzuki reaction to obtain an organic semiconductor material shown in a formula I, wherein the reaction formula is as follows:
wherein R and L are in the same range as R and L in the first aspect, and n is an integer of 0 to 3.
In the present invention, the skilled person can select the structure of the compound of formula II according to the structure of the desired target product to be synthesized, and can adjust the choice of the R group according to the structure.
For example, when all the R groups are selected from the same substituent, the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene is directly used as a raw material to react with the compound of the formula II.
When the R group is selected from different substituents, a person skilled in the art can selectively replace bromine in the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene with TMS, then react with a compound shown in the formula II with a proper equivalent, then use alkali metal bromide such as sodium bromide to react, replace TMS with bromine atom, and then react with the compound shown in the formula II, and the two used compounds shown in the formula II have different structures, so that the organic semiconductor material under the condition that the R is different substituents can be prepared.
An exemplary preparation procedure is as follows:
based on the above preparation concept, those skilled in the art can adaptively adjust the reaction steps according to the selection of R.
Preferably, the Suzuki reaction is carried out in the presence of a catalyst and an acid scavenger.
Preferably, the catalyst is tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4)。
Preferably, the molar ratio of the catalyst to the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene is (0.002 to 0.5):1, and may be, for example, 0.002:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, or 0.5: 1.
Preferably, the acid scavenger is any one of potassium phosphate, potassium carbonate, cesium carbonate, sodium carbonate or sodium bicarbonate or a combination of at least two thereof, wherein a typical but non-limiting combination includes: potassium carbonate and cesium carbonate; cesium carbonate, sodium carbonate and sodium bicarbonate, and the like.
Preferably, the molar ratio of the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene to the compound represented by the formula II is 1 (4.2-15), and may be, for example, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1: 15.
Preferably, the Suzuki reaction is carried out under the protection of a protective gas.
Preferably, the protective gas is any one of nitrogen, argon or helium.
Preferably, the suzuki reaction is carried out under protection from light.
In the invention, the reaction is carried out under the condition of keeping out of the sun, so that the reaction process is more stable, the reaction is more sufficient, and the yield is higher.
Preferably, the suzuki reaction solvent comprises any one of tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether or toluene or a combination of at least two of the above.
Preferably, the Suzuki reaction temperature is 80 to 130 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃.
Preferably, the suzuki reaction time is 20-30 h, for example, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30 h.
Preferably, the preparation method comprises the following steps:
carrying out Suzuki reaction on 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene and a compound shown in a formula II in a molar ratio of 1 (4.2-15) in the presence of a catalyst and an acid binding agent under the protection of protective gas at 80-130 ℃ in a dark condition for 20-30 h to obtain the organic semiconductor material shown in the formula I.
In a third aspect, the invention provides an OLED device, which sequentially comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode from top to bottom, wherein the electron transport layer is prepared from the organic semiconductor material substituted by the oxadiazole containing spirofluorene in the first aspect.
In the invention, when the organic semiconductor material substituted by oxadiazole containing spirofluorene is used as an electron transport layer, the organic semiconductor material is generally matched with a lithium quinoline complex LiQ according to the mass ratio of 3: 7. Wherein LiQ has the structure
Compared with the prior art, the invention has the following beneficial effects:
the oxadiazole substituted organic semiconductor material containing spirofluorene has high charge transfer capacity and high glass transition temperature, can prevent crystallization of the material in the device manufacturing process, can be used as an electronic transmission material in an OLED device, can enable the current efficiency of the OLED device to reach more than 60Cd/A, and has long service Life (LT)95) Can reach over 160h, compared with the phenanthrolineAnd compounds disclosed in the prior art have more excellent effects, greatly improve the performance of OLED devices, and have higher application value and good application prospect.
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.
The raw materials used in the following examples of the present invention are all commercially available.
Example 1
In this example, an organic semiconductor material substituted by oxadiazole containing spirofluorene was prepared by the following method
1.5g of 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene, 5g of anhydrous potassium phosphate powder, 100mL of anhydrous 1, 4-dioxane and 0.2g of Pd (PPh)3)4Adding into a 200mL three-necked bottle, vacuumizing and supplementing nitrogen for 30 min. Keeping the temperature at 101 ℃, adding 4g of 1,3, 4-oxadiazole boric acid, and carrying out reflux reaction for 24 hours in the absence of light. After cooling to room temperature, a solid precipitated, was filtered and subjected to chromatography to give 2.4g of a product (yield 47%) as compound 1.
Tg (DSC) of 107 ℃ and purity of 99.9 percent,1H NMR(400MHz，DMSO)δ7.82(s,4H),7.76(s,4H),7.60(d,4H),7.50(d,4H)。
example 2
In this example, an organic semiconductor material substituted by oxadiazole containing spirofluorene was prepared by the following method
1.5g of 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene, 4.7g of anhydrous potassium phosphate powder, 110mL of anhydrous 1, 4-dioxane and 0.3g of Pd (PPh)3)4Adding into a 200mL three-necked bottle, vacuumizing and supplementing nitrogen for 30 min. Keeping at 80 deg.C4g of 5-methyl-1, 3, 4-oxadiazole-2-boric acid is added, and the mixture is refluxed for 24 hours in a dark place. After cooling to room temperature, a solid precipitated, was filtered and subjected to chromatography to give 2.55g (yield 49%) of the product, which was compound 2.
Tg (DSC) of 112 ℃ and purity of 99.9 percent,1H NMR(400MHz，DMSO)δ7.76(s,4H),7.60(d,4H),7.50(d,4H),2.35(s,12H)。
example 3
In this example, an organic semiconductor material substituted by oxadiazole containing spirofluorene was prepared by the following method
1.5g of 2,2', 7-tribromo-7 ' -TMS-9, 9' -spirobifluorene, 4.7g of anhydrous potassium phosphate powder, 110mL of anhydrous 1, 4-dioxane and 0.3g of Pd (PPh)3)4Adding into a 200mL three-necked bottle, vacuumizing and supplementing nitrogen for 30 min. Keeping the temperature at 80 ℃, adding 3g of 1,3, 4-oxadiazole boric acid, and carrying out reflux reaction for 24h in the absence of light. Cooling to room temperature, precipitating to obtain solid, filtering, performing chromatography, reacting with sodium bromide in 1, 4-dioxane and potassium carbonate, extracting, and concentrating;
the obtained product was reacted with 5-phenyl-1, 3, 4-oxadiazole-2-boronic acid according to the above reaction procedure for further 24h to obtain a product (yield 25%) as compound 3.
Tg (DSC)115 ℃ and purity of 99.9 percent,1H NMR(400MHz，DMSO)δ7.78(s,4H),7.61(d,4H),7.44(d,3H),7.26(m,4H),7.22(m,1H)。
comparative example 1
The compound 4 is prepared by taking a phenanthroline (BPhen) organic semiconductor material as an electron transport material.
Comparative example 2
The organic semiconducting material was prepared as compound 5 according to the method disclosed in example 1 of CN103304557A
Wherein the raw material A is
Raw material B1 is
Adding 4.0mmol of compound A, 18.2 mmol of compound B and 0.01mmol of palladium tetrakis (triphenylphosphine) catalyst into a reaction bottle, vacuumizing, introducing nitrogen, circulating for 3 times, making the reaction system in an anaerobic state, and adding 2mol/L Na (50 mL of toluene) under the protection of nitrogen2CO3And (2) heating the mixed solution by 30mL of aqueous solution to carry out Suzuki coupling reaction, carrying out reflux reaction at 120 ℃ for 24 hours to obtain an organic semiconductor material compound containing spirofluorene, dissolving, adding 20mL of water, extracting with toluene for three times, washing an organic phase by using sodium chloride aqueous solution, drying, carrying out rotary evaporation to remove a solvent to obtain a crude product, and carrying out separation and purification by silica gel column chromatography to obtain a purified solid product.
Application example
The organic semiconductor materials prepared in examples 1 to 3 and comparative examples 1 to 2 were used as electron transport materials, and the organic semiconductor materials were used in application examples 1 to 5, respectively, to prepare an electron transport layer and a hole injection layer of an OLED device (NPB was used for the hole injection layer in application example 4), and one skilled in the art could prepare an OLED device according to a conventional method in the prior art. The OLED device comprises the following components in sequence from top to bottom: anode, hole injection layer, hole transport layer, luminescent layer, electron transport layer, cathode. The specific structures of the devices provided in application examples 1-5 are shown in table 1 below:
TABLE 1
Wherein F4-TCNQ has the structure of
The structure of TCTA is
Ir(ppy)3Is structured as
BPhen has the structure
The structure of NPB is
And (3) performance testing:
the OLED devices prepared in the application examples 1 to 5 were tested to measure current efficiency (LE), lighting voltage (V) and Lifetime (LT)95) Wherein the current efficiency and the lighting voltage are measured at a luminance of 1000nits and the lifetime is 40mA/cm at a current density2Calculated under the conditions, the specific results are shown in the following table 2:
TABLE 2
| Application example | Colour(s) | LE(Cd/A) | V(V) | LT95(h) |
| Application example 1 | Green colour | 66 | 3.8 | 166 |
| Application example 2 | Green colour | 69 | 3.7 | 178 |
| Application example 3 | Green colour | 62 | 3.9 | 160 |
| Application example 4 | Green colour | 53 | 5.4 | 113 |
| Application example 5 | Green colour | 55 | 4.8 | 126 |
Compared with the materials with other structures in the prior art, the organic semiconductor material substituted by oxadiazole containing spirofluorene has higher current efficiency which can reach more than 60Cd/A and longer service life which is more than 160h when being used as the material of an electronic transmission layer of an OLED device, and the performance of the device is more excellent.
The applicant states that the present invention is illustrated by the above examples to show the spirofluorene-containing oxadiazole-substituted organic semiconductor material, the preparation method and the OLED device of the present invention, but the present invention is not limited to the above detailed methods, i.e. it does not mean that the present invention must be implemented by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An oxadiazole-substituted organic semiconductor material containing spirofluorene is characterized in that the structure of the organic semiconductor material is shown as formula I:
wherein L is any one of an aromatic ring, an aromatic heterocyclic ring, a substituted aromatic ring or a substituted aromatic heterocyclic ring, and the value of n is an integer of 0-3;
r is independently selected from hydrogen, deuterium, substituted C6～C60Aromatic ring, C6～C60Aromatic ring, substituted C5～C60Aromatic heterocyclic ring, C5～C60Aromatic heterocyclic ring, C1～C50Alkyl or substituted C1～C50Any one or a combination of at least two of the alkyl groups of (a).
2. The organic semiconductor material according to claim 1, wherein the organic semiconductor material is any one of the following structures:
3. the organic semiconductor material according to claim 1 or 2, wherein the organic semiconductor material has a structure of
4. A method for the preparation of an organic semiconducting material according to any of claims 1-3, characterized in that the method comprises the steps of: 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene and a compound of a formula II are subjected to Suzuki reaction to obtain an organic semiconductor material shown in a formula I, wherein the reaction formula is as follows:
wherein R and L are in the same range as R and L described in claim 1, and n is an integer of 0 to 3.
5. The method according to claim 4, wherein the Suzuki reaction is carried out in the presence of a catalyst and an acid scavenger;
preferably, the catalyst is tetrakis (triphenylphosphine) palladium;
preferably, the molar ratio of the catalyst to the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene is (0.002-0.5): 1;
preferably, the acid-binding agent is any one or a combination of at least two of potassium phosphate, potassium carbonate, cesium carbonate, sodium carbonate or sodium bicarbonate.
6. The preparation method according to claim 4 or 5, wherein the molar ratio of the 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene to the compound represented by the formula II is 1 (4.2-15).
7. The method according to any one of claims 4 to 6, wherein the Suzuki reaction is carried out under protection of a protective gas;
preferably, the protective gas is any one of nitrogen, argon or helium;
preferably, the suzuki reaction is carried out under protection from light.
8. The method according to any one of claims 4 to 7, wherein the suzuki reaction solvent comprises any one or a combination of at least two of tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, or toluene;
preferably, the Suzuki reaction temperature is 80-130 ℃;
preferably, the Suzuki reaction time is 20-30 h.
9. The method according to any one of claims 4 to 8, characterized by comprising the steps of:
carrying out Suzuki reaction on 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene and a compound shown in a formula II in a molar ratio of 1 (4.2-15) in the presence of a catalyst and an acid binding agent under the protection of protective gas at 80-130 ℃ in a dark condition for 20-30 h to obtain the organic semiconductor material shown in the formula I.
10. An OLED device, which comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode from top to bottom in sequence, wherein the electron transport layer is prepared from the organic semiconductor material substituted by oxadiazole containing spirofluorene according to claims 1-3.
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