CN115490568A - Polyaryl spirobifluorene and application thereof in organic electroluminescent device - Google Patents
Polyaryl spirobifluorene and application thereof in organic electroluminescent device Download PDFInfo
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- CN115490568A CN115490568A CN202110682942.2A CN202110682942A CN115490568A CN 115490568 A CN115490568 A CN 115490568A CN 202110682942 A CN202110682942 A CN 202110682942A CN 115490568 A CN115490568 A CN 115490568A
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- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 125000005264 aryl amine group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 4
- 238000001816 cooling Methods 0.000 claims 3
- 125000003107 substituted aryl group Chemical group 0.000 claims 3
- 238000010791 quenching Methods 0.000 claims 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 claims 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims 1
- 125000001769 aryl amino group Chemical group 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 description 16
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 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 10
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 10
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 10
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 9
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 2
- VOZBMWWMIQGZGM-UHFFFAOYSA-N 2-[4-(9,10-dinaphthalen-2-ylanthracen-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC=C(C=2C=C3C(C=4C=C5C=CC=CC5=CC=4)=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C3=CC=2)C=C1 VOZBMWWMIQGZGM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 spirobifluorene compound Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/72—Spiro hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/28—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by ring closure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
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- 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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to the field of organic electroluminescent materials, in particular to a novel 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraarylspirobifluorene structure and application of the material in an organic electroluminescent display device. The 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene derivatives have the structural formula shown in formula I:
Description
Technical Field
The invention belongs to the technical field of spirobifluorene derivatives, and particularly relates to structures, preparation methods and applications of 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene.
Background
Organic Light Emitting Diodes (OLEDs) have been of interest to the scientific and industrial community as a new technology in the display and lighting areas. Since Deng Qingyun et al prepared the first organic electroluminescent device in 1987, the structure and efficiency of the OLED device have been greatly improved and improved. The doped device, i.e., the luminescent molecules are dispersed in the host material, can avoid the concentration quenching effect of the luminescent material to improve the luminous efficiency of the device, and can also slow down the aging process of the device to improve the service life of the device. In addition, the adoption of doped luminescence can also increase the flexibility of device design, thereby enabling the application prospect of the luminescent material to be wider.
In recent years, research on host materials in organic electroluminescent devices has been underway, and host materials in OLED devices must have good carrier transport properties and can form pinhole-free thin films. By comprehensively considering the structural characteristics of the luminescent material and the device, the main material needs to have the following properties: 1. the HOMO/LUMO energy levels of the dopant material are embedded in the host material. 2. The emission spectrum of the host material has an effective overlap with the absorption spectrum of the dopant material. 3. The host material has a higher triplet energy level to prevent reverse transfer of triplet energy from the dopant material to the host material. 4. The positive and negative charge carrier transport in the host material needs to be balanced to confine the exciton recombination zone in the light emitting layer of the device. 5. The HOMO/LUMO energy level of the host material is matched with the energy level of the adjacent hole transport layer and the electron transport layer so as to reduce the injection barrier and lower the starting voltage of the device. Therefore, the synthesis of a host material with matching energy levels and high efficiency is challenging.
Disclosure of Invention
The invention aims to provide a series of novel main materials taking 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene structures as central skeletons.
The 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene compounds described in the present invention have the structures shown in formula I:
wherein Ar represents any one of substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 1 to 30 carbon atoms, substituted or unsubstituted arylamine with 6 to 30 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted arylalkylsilyl with 6 to 30 carbon atoms, nitro, cyano and halogen.
Preferably, the organic electroluminescent host material includes, but is not limited to, the following structural formula:
the second objective of the present invention is to provide a preparation method of the above organic electroluminescent host material, wherein the reaction formula is as follows:
the third purpose of the invention is to provide an organic electroluminescent main body material based on 1,3-diarylspirobifluorene, 1,6-diarylspirobifluorene, 1,3,6-triarylspirobifluorene, 1,3,7-triarylspirobifluorene and 1,3,6,8-tetraarylspirobifluorene, which is used as a main body material of a luminescent layer and is applied to the field of manufacturing organic electroluminescent devices.
The present invention includes, but is not limited to, the following 1,3-diarylspirobifluorenes, 1,6-diarylspirobifluorenes, 1,3,6-triarylspirobifluorenes, 1,3,7-triarylspirobifluorenes, 1,3,6,8-tetraarylspirobifluorene structures:
the substituents R are each the same or different and are, independently of one another, one or more substituents selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 24 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having l to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon-6 to 30 carbon-atom group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted silyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, and an arylamine group.
The prepared organic electroluminescent device comprises an ITO conductive glass substrate (anode), a hole injection layer (HAT-CN), a hole transport layer (TAPC), an electron blocking layer (TCTA, mCP), a luminescent layer (FIrPic doped in the organic electroluminescent main body material), an electron transport layer (TmPyPB), electron injection (LiF) and a cathode layer (Al) which are sequentially superposed. The organic electroluminescent device is prepared by a vacuum evaporation method. Some of the organic compounds used in the device have the following molecular structural formula.
The beneficial effects of the invention are:
1. the polyarylation spirobifluorene compound provided by the invention has good photoelectric property and thermal stability, and HOMO and LUMO energy levels are easy to allocate, so that the polyarylation spirobifluorene compound is suitable for various luminescent materials, can improve the exciton utilization rate and reduce the efficiency roll-off, and has good photoelectric property.
2. The 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene provided by the invention can be used as a main material of blue phosphorescent OLEDs due to high triplet state energy level; 1,3-diarylspirobifluorenes, 1,6-diarylspirobifluorenes, 1,3,6-triarylspirobifluorenes, 1,3,6,8-tetraarylspirobifluorenes can also be used as host materials for green phosphorescent OLEDs; 1,3,7-triarylspirobifluorene can be used as a host material to sensitize red phosphorescent materials.
3. The main body material prepared by the invention can be a Yu Min chemical Thermal Activation Delayed Fluorescence (TADF) material, is used for preparing OLED devices, has good device performance, realizes high efficiency, reduces efficiency roll-off, and has good industrial application prospect.
4. The polyaryl spirobifluorene prepared by the method has larger application potential in the aspect of all-carbon framework main body materials, provides a new synthetic thought for the all-carbon framework main body materials, and shows the superiority of C-H activation as a synthetic strategy in the aspect of developing photoelectric materials.
Drawings
FIG. 1 NMR spectrum H of Compound 3.
FIG. 2 NMR spectra C of Compound 3
FIG. 3 NMR H spectrum of Compound B4.
FIG. 4 NMR spectrum C of Compound B4.
FIG. 5 Single Crystal Structure of Compound B1.
FIG. 6 Single Crystal Structure of Compound B2.
FIG. 7 Single Crystal Structure of Compound B3.
FIG. 8 is a schematic view of the structure of an organic electroluminescent device of the present invention.
Detailed Description
For a better understanding of the present disclosure, the following examples are set forth to illustrate, but are not to be construed to limit the scope of the present disclosure.
Example 1: preparation of Compound B4
Under nitrogen atmosphere, [ Cp IrCl ] was added to a Schlenk tube with a magnetic stirrer 2 ] 2 (3.9mg,2.5mol％)、AgSbF 6 (6.9mg,10mol％)、Ag 2 O (92.7mg, 2.0 eq), pivOH (20.4mg, 1.0 eq), p-phenylbenzoic acid (1,0.2mmol), diaryliodonium salt (2,0.42mmol) and DCE (1.0 mL). The resulting mixture was stirred at 120-150 ℃ for 12-24 hours, then 5mL CH was used 2 Cl 2 And (6) diluting. The solution was filtered through a pad of celite and 10-25mL CH 2 Cl 2 And (6) washing. The filtrate was concentrated in vacuo and chromatographed on silica gel (petrol ether/CH) 2 Cl 2 =4/1,v/v) purification of the residue to provide the desired product 3. 1 H NMR(400MHz,CDCl 3 ):δ＝7.87(s,1H),7.78-7.67(m,11H),7.65-7.61(m,2H),7.54-7.45(m,8H),7.39(t,J＝7.2Hz,2H)ppm. 13 C NMR(100MHz,CDCl 3 ):δ＝192.53,147.38,146.24,142.51,142.28,142.08,141.17,140.82,139.90,139.84,136.37,135.50,132.99,130.30,129.68,129.00,128.93,128.80,128.78,128.61,127.89,127.38,127.23,127.20,126.82,126.70,122.66,120.38,118.08ppm.HRMS(ESI + ) Calculated value C 37 H 25 O[M+H] + 485.1900, found 485.1905.3, the nuclear magnetic hydrogen spectrum is shown in figure 1, and the nuclear magnetic carbon spectrum is shown in figure 2.
Into a Schlenk tube with a magnetic stirrer under a nitrogen atmosphere2-bromobiphenyl (1.1 eq), 40mL of anhydrous tetrahydrofuran and cooled to-78 deg.C, followed by the slow dropwise addition of 1.0 eq of a 2.5mol/L n-butyllithium solution. The reaction system was stirred for one hour at-78 ℃ and then 1.0 equivalent of reactant 3 dissolved in 20mL of anhydrous tetrahydrofuran was slowly added dropwise. The reaction was then heated to 75 ℃ and stirred for 24 hours. After the reaction was complete, it was cooled to room temperature and quenched with dilute ammonium chloride solution. The reaction system was extracted with ethyl acetate and dried by adding anhydrous sodium sulfate. After removal of the solvent, the remaining solid was dissolved using 100mL of 1, 2-dichloroethane and 5.0 equivalents of boron trifluoride in ethyl ether were slowly added. The reaction was stirred at room temperature for three hours, quenched by addition of methanol, and the solvent removed, and purified by silica gel column chromatography (petroleum ether/CH) 2 Cl 2 =8/1,v/v) purification of the residue to provide the desired product 4. 1 H NMR(400MHz,CDCl 3 ):δ＝8.13(s,1H),8.01(d,J＝8.0Hz,1H),7.75(d,J＝7.6Hz,2H),7.65(d,J＝8.0Hz,1H),7.52-7.44(m,6H),7.43-7.34(m,6H),7.32-7.26(m,3H),7.22(t,J＝7.4Hz,3H),7.09(t,J＝7.6Hz,2H),6.91-6.85(m,5H),6.23(d,J＝8.4Hz,2H)ppm. 13 C NMR(100MHz,CDCl 3 ):δ＝150.14,148.12,145.37,142.66,142.17,141.47,141.11,140.97,140.87,140.84,140.53,140.46,138.55,137.60,128.83,128.66,128.63,128.53,128.21,127.44,127.31,127.25,127.12,127.03,127.02,126.98,126.76,125.29,123.97,122.58,120.31,119.78,117.59,65.61ppm.HRMS(ESI + ) Calculated value C 49 H 33 [M+H] + 621.2577, found 621.2577. The nuclear magnetic hydrogen spectrum of B4 is shown in figure 3, and the nuclear magnetic carbon spectrum is shown in figure 4.
Examples 2 to 4: the preparation of compounds B1, B2, B3 is referred to example 1. The single crystal structure of B1 is shown in FIG. 5, the single crystal structure of B2 is shown in FIG. 6, and the single crystal structure of B3 is shown in FIG. 7.
Application examples of the organic electroluminescent device:
the invention selects the compounds B1, B2, B3 and B4 and the commercially available 4,4' -bis (9H-carbazole-9-yl) biphenyl (CBP) as the main material to manufacture the organic electroluminescent device, and uses the commercially available phosphorescence or thermal activation delayed fluorescence material as the luminescent material. With reference to fig. 8, the organic electroluminescent device comprises, from bottom to top, an ITO conductive glass substrate (1), a hole injection layer (2), a hole transport layer (3), a light emitting layer (4), an electron transport layer (5), an electron injection layer (6), and a cathode layer (7). It should be understood that the device implementation and results are merely for better explanation of the present invention and are not meant to be a limitation of the present invention.
Application example 1
The phosphorescent organic electroluminescent device was prepared as follows:
1. cleaning of ITO (indium tin oxide) glass: washing with alkali and deionized water in sequence, drying in a vacuum drying oven, and treating in a plasma cleaner for 10 minutes;
2. sequentially vacuum evaporating a hole injection layer HAT-CN (10 nm), a hole transport layer TAPC (30 nm), an electron blocking layer TCTA (10 nm), an exciton blocking layer mCP (10 nm) on the anode ITO glass, wherein the evaporation rate is 0.1nm/s;
3. vacuum evaporation of light-emitting layer (3%) Ir (mphmp) on top of the electron blocking layer 2 tmd: b4, the evaporation rate is 0.1nm/s, and the evaporation thickness is 20nm;
4. vacuum evaporating an electron transport layer TmPyPb (40 nm) on the luminescent layer, wherein the evaporation rate is 0.1nm/s;
5. vacuum evaporating an electron injection layer LiF (0.8 nm) on the electron transport layer, wherein the evaporation rate is 0.08nm/s;
6. a cathode Al (100 nm) was vacuum-deposited on the electron injection layer at a deposition rate of 0.1nm/s.
The device structure adopted comprises:
blue light: ITO/HAT-CN (10 nm)/TAPC (30 nm)/TCTA (10 nm)/mCP (10 nm)/B1: 15wt%/Flrpic, (20 nm)/TmPyPB (50 nm)/LiF (0.8 nm)/Al (100 nm);
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(10nm)/mCP(10nm)/B2:15wt％Flrpic,(20nm)/TmPyPB(40nm)/LiF(0.8nm)/Al(100nm)。
green light: ITO/HAT-CN (10 nm)/TAPC (30 nm)/TCTA (10 nm)/B2: 15wt% Ir (ppy) 3 ,(20nm)/TmPyPB(60nm)/LiF(0.8nm)/Al(100nm)；
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(10nm)/B3:15wt％Ir(ppy) 3 ,(20nm)/TmPyPB(50nm)/LiF(0.8nm)/Al(100nm)；
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(10nm)/B4:15wt％Ir(ppy) 3 ,(20nm)/TmPyPB(40nm)/LiF(0.8nm)/Al(100nm)。
Red light: ITO/HAT-CN (10 nm)/TAPC (30 nm)/TCTA (10 nm)/mCP (10 nm)/B3: 3wt% 2 tmd,(20nm)/TmPyPB(40nm)/LiF(0.8nm)/Al(100nm)；
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(10nm)/mCP(10nm)/B4:3wt％Ir(mphmp) 2 tmd,(20nm)/TmPyPB(40nm)/LiF(0.8nm)/Al(100nm)；
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(10nm)/mCP(10nm)/CBP:3wt％Ir(mphmp) 2 tmd,(20nm)/TmPyPB(40nm)/LiF(0.8nm)/Al(100nm)。
Comparative example
An organic electroluminescent device was fabricated according to the method of application example 1, except that compound CBP was used as the light-emitting material instead of compound B4. The test results of the resulting devices are shown in table I.
The compound B4 is used as a main body material of the device, and the test results of the obtained device are shown in the table I.
TABLE I
For comparison, the present invention fabrication used CBP as the reference device. As shown in Table 1, the current efficiency of the CBP based device is 29.9lm/W, and the maximum EQE is 19.2%. The organic electroluminescent device prepared based on the material shows better device performance, the maximum power efficiency is 44.4lm/W, the maximum EQE is 27.3%, and compared with a comparative device CBP, the organic electroluminescent device shows excellent characteristics in the aspects of current efficiency and device efficiency.
The results of the performance tests of the two to seven devices produced in application examples 2-7 are shown in table II.
TABLE II
Application example 2
The thermal activation delayed fluorescence organic electroluminescent device is prepared according to the following method:
1. cleaning of ITO (indium tin oxide) glass: washing with alkali and deionized water in sequence, drying in a vacuum drying oven, and treating in a plasma cleaner for 10 minutes;
2. sequentially vacuum evaporating a hole injection layer HAT-CN (10 nm) and a hole transport layer alpha-NPD (60 nm) on the anode ITO glass, wherein the evaporation rate is 0.1nm/s;
3. vacuum evaporation of a light-emitting layer on the electron blocking layer, (8%) B1:4CzIPN, the evaporation rate is 0.1nm/s, and the evaporation thickness is 30nm;
4. vacuum evaporating a hole blocking layer mBPDBT (5 nm) and an electron transport layer ZADN (40 nm) on the luminescent layer, wherein the evaporation rate is 0.1nm/s;
5. vacuum evaporating an electron injection layer Liq (2 nm) on the electron transport layer, wherein the evaporation rate is 0.08nm/s;6. a cathode Al (120 nm) was vacuum-deposited on the electron injection layer at a deposition rate of 0.1nm/s.
The device structure is as follows: ITO/HAT-CN (10 nm)/α -NPD (60 nm)/B4: 4CzIPN (8 wt%,30 nm)/mBPDBT (5 nm)/ZADN (40 nm)/Liq (2 nm)/Al (120 nm).
The above description is only a few embodiments of the present invention, and is not intended to limit the present invention, and any modifications, substitutions, etc. within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (6)
1. A novel structure of electroluminescent main body material taking 1,3-diaryl spirobifluorene, 1,6-diaryl spirobifluorene, 1,3,6-triaryl spirobifluorene, 1,3,7-triaryl spirobifluorene and 1,3,6,8-tetraaryl spirobifluorene as central molecular frameworks and application of the material in an organic electroluminescent display device are disclosed, and the structural characteristics of the electroluminescent main body material are shown in formula I
2. The electroluminescent host material according to claim 1, wherein Ar represents any one of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylsilicon group having 6 to 30 carbon atoms, a nitro group, a cyano group, and a halogen.
3. An electroluminescent host material according to claims 1 and 2, wherein Ar is an aryl group and a substituted aryl group, and the structure is represented by formula II, and the substituents R are the same or different and are independently selected from hydrogen, heavy hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 24 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having l to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, a substituted cyano group having 1 to 30 carbon atoms, a substituted aryl group having 1 to 30 carbon atoms, a cyano group, or unsubstituted aryl group having 1 to 30 carbon atoms, a cyano group, or a substituted aryl group having 1 to 30 carbon atoms, or unsubstituted aryl group having one or substituted cyano group
4. A method for preparing polyaryl spirobifluorene electroluminescent host molecules as claimed in claims 1,2 and 3, comprising the steps of:
1) Under nitrogen atmosphere, [ Cp IrCl ] was added to a Schlenk tube with a magnetic stirrer 2 ] 2 、AgSbF 6 、Ag 2 O, pivOH, benzoic acid derivative (1), diaryl iodonium salt (2) and DCE, stirring the resulting mixture at 80-150 deg.c for 6-48 hours, cooling to room temperature after completion of the reaction, and adding CH 2 Cl 2 Diluting, filtering the solution through Celite and adding CH 2 Cl 2 Washing, concentrating the filtrate in vacuo and purifying the residue by silica gel column chromatography to provide the desired product 3;
2) Adding 2-bromobiphenyl, anhydrous tetrahydrofuran and cooling to-78 ℃ under a nitrogen atmosphere, then slowly dropping 1.0 equivalent of a butyllithium solution, after stirring the reaction system at-78 ℃ for one hour, slowly dropping 1.0 equivalent of a reactant 3 dissolved in anhydrous tetrahydrofuran, then heating the reaction system to 50-100 ℃ and stirring for 24 hours, after the reaction is finished, cooling to room temperature and quenching with a dilute ammonium chloride solution, extracting the reaction system with ethyl acetate and drying with anhydrous sodium sulfate, after removing the solvent, dissolving the remaining solids with 1,2-dichloroethane and slowly adding 5.0 equivalents of a boron trifluoride ether solution, after the reaction is finished, stirring at room temperature for three hours, adding methanol to quench and removing the solvent to purify the residue by silica gel column chromatography to provide the desired product 4.
5. The organic electroluminescent device as claimed in claims 1 to 3, wherein the organic electroluminescent device is made of polyarylation spirobifluorene as a main material, wherein the organic electroluminescent device comprises an ITO conductive glass substrate (1), a hole injection layer (2), a hole transport layer (3), a luminescent layer (4), an electron transport layer (5), an electron injection layer (6) and a cathode layer (7) from bottom to top.
6. The organic electroluminescent device prepared by using polyaryl spirobifluorene as a main material according to the claim 5, is characterized in that the maximum power efficiency is 44.4lm/W, and the maximum External Quantum Efficiency (EQE) is 27.3%.
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| US20180026187A1 (en) * | 2015-02-09 | 2018-01-25 | Duk San Neolux Co., Ltd. | Novel compound for organic electric element, organic electric element using the same, and electronic device comprising same |
| CN108698978A (en) * | 2016-02-23 | 2018-10-23 | 默克专利有限公司 | Material for organic electroluminescence device |
| CN109195951A (en) * | 2016-06-03 | 2019-01-11 | 默克专利有限公司 | Material for organic electroluminescence device |
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