CN115974702B - Spiro compound and application thereof - Google Patents
Spiro compound and application thereof Download PDFInfo
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- CN115974702B CN115974702B CN202310114497.9A CN202310114497A CN115974702B CN 115974702 B CN115974702 B CN 115974702B CN 202310114497 A CN202310114497 A CN 202310114497A CN 115974702 B CN115974702 B CN 115974702B
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- 150000003413 spiro compounds Chemical class 0.000 title claims abstract description 25
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 230000005525 hole transport Effects 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 7
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 75
- 239000000463 material Substances 0.000 abstract description 49
- 238000000859 sublimation Methods 0.000 abstract description 19
- 230000008022 sublimation Effects 0.000 abstract description 19
- 230000008018 melting Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 6
- 229920001621 AMOLED Polymers 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 45
- 238000003786 synthesis reaction Methods 0.000 description 45
- 238000000746 purification Methods 0.000 description 26
- -1 adamantyl fluorene Chemical compound 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 239000007858 starting material Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 8
- 125000004404 heteroalkyl group Chemical group 0.000 description 7
- 125000001072 heteroaryl group Chemical group 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101100457453 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MNL1 gene Proteins 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000005104 aryl silyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 3
- 101100451713 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) HTL1 gene Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical class C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- NHFDIUPJVYYTLG-UHFFFAOYSA-N carbononitridic isocyanide Chemical compound [C-]#[N+]C#N NHFDIUPJVYYTLG-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005549 heteroarylene group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 125000004134 1-norbornyl group Chemical group [H]C1([H])C([H])([H])C2(*)C([H])([H])C([H])([H])C1([H])C2([H])[H] 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000008358 core component 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UAJUXJSXCLUTNU-UHFFFAOYSA-N pranlukast Chemical compound C=1C=C(OCCCCC=2C=CC=CC=2)C=CC=1C(=O)NC(C=1)=CC=C(C(C=2)=O)C=1OC=2C=1N=NNN=1 UAJUXJSXCLUTNU-UHFFFAOYSA-N 0.000 description 1
- 229960004583 pranlukast Drugs 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The spiro compound has a structure shown in a formula (1). The spiro compound provided by the invention has the advantages of high photo-electric stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of devices and the like, and can be used in organic electroluminescent devices. Meanwhile, the material has a lower melting point, and is favorable for material evaporation stability as a melting type material. The compound can be used as a hole injection and transmission material and has the possibility of being applied to AMOLED industry.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material suitable for an organic electroluminescent device, and particularly relates to a spiro compound and application thereof.
Background
At present, an organic electroluminescent device (OLED) as a new generation display technology has gained more and more attention in the aspects of display and illumination technologies, and has a very wide application prospect. However, the performance of OLED devices, such as luminous efficiency, driving voltage, lifetime, etc., is still in need of continued enhancement and improvement as compared to the market application requirements.
In general, the OLED device has a basic structure in which various organic functional material films with different functions are interposed between metal electrodes, like a sandwich structure, holes and electrons are injected from both electrodes under the driving of current, and after a certain distance, the holes and electrons are recombined in a light emitting layer and released in the form of light or heat, thereby generating light emission of the OLED. However, the organic functional material is a core component of the organic electroluminescent device, and thermal stability, photochemical stability, electrochemical stability, quantum yield, film forming stability, crystallinity, color saturation and the like of the material are all main factors affecting the performance of the device.
In order to obtain an organic light-emitting device with excellent performance, the selection of materials is particularly important, and the organic light-emitting device comprises not only an emitter material with a light-emitting effect, but also functional materials such as a hole injection material, a hole transport material, a main material, an electron transport material, an electron injection material and the like which mainly act as carrier injection and transport in the device, and the selection and optimization of the functional materials can improve the transport efficiency of holes and electrons, so that the holes and electrons in the device are balanced, and the voltage, the light-emitting efficiency and the service life of the device are improved.
Patent document 1 (CN 103108859B) describesThe structure of the spirofluorene aromatic amine is used as a hole transport material, the material provides better device performance, but the service life of the device, particularly the service life of a blue light-emitting device, needs to be further improved, and the transverse hole mobility of the material needs to be further improved so as to provide better low gray-scale color purity of OLED products;patent document 2 (CN 103641726B) describes +.>The structure of the spirofluorene aromatic amine is used as a second hole transport material, and the device performance of the material needs to be greatly improved, in particular to the device efficiency; patent document 3 (CN 111548278A) describes +.>The aromatic amine of the spirofluorene aromatic amine contains substituent groups such as alkyl, deuterium, cycloalkyl and the like which are used as hole transport materials, and the device performance of the materials is still to be further improved, in particular the service life of the devices; patent document 4 (CN 114835591 a) describes +.>The aromatic amine hole transport material containing unilateral cycloalkyl substituted diphenyl fluorene has the advantages that the device performance of the material is still to be further improved, particularly the device efficiency, and meanwhile, the reported compound has a higher melting point and is not suitable for being used as a melting type material in industry. Patent document 5 (CN 112110825B) describesThe structure is characterized by taking adamantyl fluorene as a core structure, and is different from the core spirofluorene structure of the invention. Patent document 6 (CN 107459466B) describes +.>The diphenylfluorene structure is also to be improved in terms of efficiency and lifetime.
Disclosure of Invention
The invention aims to solve the defects and provide a high-performance organic electroluminescent device and a spiro compound material capable of realizing the organic electroluminescent device.
The spiro compound has a structure shown in a formula (1). The spiro compound provided by the invention has the advantages of high photo-electric stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of devices and the like, and can be used in organic electroluminescent devices. Meanwhile, the material has a lower melting point, and is favorable for material evaporation stability as a melting type material. The compound can be used as a hole injection and transmission material and has the possibility of being applied to AMOLED industry.
A spiro compound has a structure shown in formula (1),
wherein the R is 1 ，R 2 Substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
wherein ring A is selected from the group consisting of substituted or unsubstituted C3-C20 saturated aliphatic rings
Wherein R is a -R d Is a substituent on the phenyl ring independently selected from deuterium, halogen, cyano, hydroxy, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or two adjacent groups may be linked to each other to form an aliphatic or aromatic cyclic structure;
wherein L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene;
wherein Ar is independently selected from the group consisting of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
wherein m, n, p, q is independently selected from 0 or an integer from 1 to 4;
wherein at least one of the heteroalkyl, heterocycloalkyl, and heteroaryl groups contains a O, N or S heteroatom;
the substitution is by deuterium, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C1-C4 alkyl substituted C6-C10 aryl, C1-C6 alkyl substituted amino, cyano, isonitrile or phosphino, wherein the number of substitutions is from monosubstituted to the maximum number of substitutions.
As a preferred spiro compound, one of the structures represented by the formulae (2) - (5),
wherein the definition of the remaining symbols is the same as described above.
As a preferred spiro compound, it has a structure represented by formula (2) or formula (3), R 1 And R is R 2 The same or different.
As a preferred spiro compound, wherein L is as defined in the formula (2) -formula (5) 1 、L 2 、L 3 Preferably a single bond.
As a preferred spiro compound, structures represented by the formulas (6) to (9):
as a preferred spiro compound, wherein ring a of the spiro compound is one of the following aliphatic rings:
as preferred spiro compounds, R 1 And R is R 2 Ar is selected from substituted or unsubstituted phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl or carbazolyl, wherein the substitution is substituted by deuterium, F, cl, br, C-C10 aryl, C1-C6 alkyl, C3-C6 cycloalkyl.
The R is 1 ，R 2 Is a substituted or unsubstituted C1-C10 alkyl, substituted or unsubstitutedC3-C20 cycloalkyl.
As preferred spiro compounds, preference is given to those of one of the following formulae, or the corresponding partial or complete deuteration or fluorination,
one of the purposes of the invention is also the application of the spiro compound in an organic electroluminescent device.
Another object of the present invention is to provide the above spiro compound as a hole injection layer and/or a hole transport layer of an organic electroluminescent device.
The material has the advantages of high light and electricity stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of the device and the like, and can be used in an organic electroluminescent device. In particular, as a hole injection/transport material, there is a possibility of application to the AMOLED industry.
Drawings
FIG. 1 is a deuterated chloroform solution of compound CPD004 of the present invention 1 A HNMR spectrum of the sample,
FIG. 2 is a deuterated chloroform solution of compound CPD017 of the present invention 1 HNMR spectrogram
Detailed Description
The compound of the invention, a spiro compound, has a structure shown in a formula (1),
wherein the R is 1 ，R 2 Substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
wherein ring A is selected from the group consisting of substituted or unsubstituted C3-C20 saturated aliphatic rings
Wherein R is a -R d Independently selected from hydrogen, deuterium, halogen, cyano, hydroxy, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or two adjacent groups may be linked to each other to form an aliphatic or aromatic cyclic structure;
wherein L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene;
wherein Ar is independently selected from the group consisting of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
wherein m, n, p, q is independently selected from 0 or an integer from 1 to 4;
wherein the heteroalkyl and heteroaryl groups contain at least one O, N or S heteroatom;
the substitution is by deuterium, F, cl, br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, cyano, isonitrile or phosphino, wherein the number of substitutions is from monosubstituted to the maximum number of substitutions.
Examples of the groups of the compound represented by the formula (1) are described below.
In the present specification, "the carbon number a to b" in the expression "X group of a carbon number a to b which is substituted or unsubstituted" means the carbon number in the case where the X group is unsubstituted, and does not include the carbon number of the substituent in the case where the X group is substituted.
The C1 to C10 alkyl group is a linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and its isomer, an n-hexyl group and its isomer, an n-heptyl group and its isomer, an n-octyl group and its isomer, an n-nonyl group and its isomer, an n-decyl group and its isomer, and the like, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, more preferably a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl groups, and preferably cyclopentyl and cyclohexyl groups.
Examples of the C2-C10 alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, and 3-hexatrienyl, and allyl is preferred.
The C1-C10 heteroalkyl group is a linear or branched alkyl group or cycloalkyl group containing an atom other than hydrocarbon, examples thereof include a mercapto methyl group, a methoxy methyl group, an ethoxy methyl group, a t-butoxy methyl group, N, N-dimethylmethylalkyl, epoxybutanoyl, epoxypentanoyl, epoxyhexanoyl, and the like, preferably methoxymethylalkyl, epoxypentanoyl, and the like.
Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, phenanthryl, naphthacene, pyrenyl, droyl, benzo [ c ] phenanthryl, benzo [ g ] droyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, tetrabiphenyl, and fluoranthenyl, and phenyl and naphthyl are preferable.
Specific examples of heteroaryl groups include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, quinolinyl, isoquinolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thienyl, benzothienyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, quinazolinyl, and the like, and preferably pyridyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadicarbazolyl, azacarbazolyl, and the like.
The following examples are merely for the purpose of facilitating understanding of the technical invention and should not be construed as a specific limitation of the invention.
The starting materials and solvents, etc., involved in the synthesis of the compounds of the present invention are available from suppliers well known to those skilled in the art of Alfa, acros, etc.
EXAMPLE 1 Synthesis of Compound CPD003
Synthesis of Compound CPD003-3
Compound CPD003-1 (20.00 g,66.84 mmol), CPD003-2 (12.44 g,73.53 mmol), tris (dibenzylideneacetone) dipalladium (1.84 g,2.01 mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (6.37 g,13.37 mmol), sodium t-butoxide (9.63 g,100.26 mmol), dried toluene (300 ml) were added to a 1000ml three port round bottom flask, nitrogen was replaced three times, and the temperature was raised to 100℃for 3 hours. TLC (ethyl acetate: n-hexane=1:20 as developing solvent) was used up to monitor the consumption of starting material CPD 003-1.
After cooling to room temperature, toluene (400 ml) was added, washed with deionized water (3×200 ml), separated, purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane=1:25 as eluent), and after elution, concentrated under reduced pressure at 60 ℃ to give CPD003-3 (22.03 g, purity: 99.77%, yield: 85.06%) as a white solid, mass spectrum: 388.22 (M+H).
Synthesis of Compound CPD003
CPD003-4 (23.00 g,45.31 mmol), CPD003-3 (17.91 g,46.22 mmol), tris (dibenzylideneacetone) dipalladium (0.83 g,0.91 mmol), 50% by mass of a solution of tri-tert-butylphosphine in toluene (3.67 g,9.06 mmol), sodium tert-butoxide (6.53 g,67.97 mmol) and dry toluene (350 ml) were added to a 1000ml three-necked round bottom flask, nitrogen was replaced three times with stirring at room temperature, then the temperature was raised to 110℃and the reaction was monitored by TLC (ethyl acetate: n-hexane=1:20 as a developing solvent) for 4 hours, and the consumption of the starting material CPD003-4 was completed.
Cooling to room temperature, adding toluene (400 ml), washing with deionized water (3×300 ml), separating, purifying by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane=1:15 as eluent), eluting, and concentrating at 70deg.C under reduced pressure to obtain white solid; 150ml of methanol was added, and the mixture was slurried at an oil temperature of 65℃for 1 hour, suction-filtered, 50ml of methanol was used to wash the cake, and vacuum-dried at 90℃for 8 hours to give CPD003 (27.79 g, purity: 99.90%, yield: 75.34%) as a white solid. Sublimation purification of 27.79g of crude CPD003 gave sublimated pure CPD003 (22.51 g, purity: 99.95%, yield: 81.00%), mass spectrum: 814.24 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.67(m,1H),7.55-7.47(m,3H),7.44(d,J＝10.0Hz,2H),7.39(s,1H),7.24(d,J＝3.1Hz,2H),7.15-7.11(m,1H),7.07-6.90(m,13H),6.86-6.80(m,2H),6.76-6.65(m,3H),6.63-6.59(m,1H),1.87-1.78(m,2H),1.67-1.59(m,2H),1.42-1.38(m,4H),1.20(s,18H).
EXAMPLE 2 Synthesis of Compound CPD004
Synthesis of Compound CPD004-2
The synthesis and purification method of the reference compound CPD003-3 only needs to change the corresponding original material to obtain the target compound CPD004-2 (23.24 g, purity: 99.71%, yield: 81.01%), mass spectrum: 402.22 (M+H).
Synthesis of Compound CPD004
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD004 (16.34 g, purity: 99.92%, yield: 75.63%) was obtained as the objective compound. Sublimation purification of 16.34g of crude CPD004 gave sublimated pure CPD004 (12.51 g, purity: 99.93%, yield: 76.56%), mass spectrum: 828.46 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.72(d,J＝7.5Hz,1H),7.60-7.53(m,4H),7.49(d,J＝7.5Hz,1H),7.33-7.13(m,10H),7.03-6.92(m,7H),6.79(s,1H),6.73(s,2H),6.63(d,J＝7.5Hz,1H),6.57(d,J＝8.4Hz,1H),6.44(s,1H),1.74-1.57(m,5H),1.49-1.38(m,5H),1.21(s,18H).
EXAMPLE 3 Synthesis of Compound CPD014
Synthesis of Compound CPD014
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD014 (18.05 g, purity: 99.92%, yield: 73.06%) was obtained as the objective compound. Sublimation purification of 18.05g of crude CPD014 gave sublimated pure CPD014 (14.44 g, purity: 99.92%, yield: 80.00%), mass Spectrometry: 838.16 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.73-7.69(m,1H),7.53-7.52(m,2H),7.50-7.46(m,9.1Hz,3H),7.16(d,J＝3.1Hz,2H),7.11-6.91(m,13H),6.89-6.86(m,5H),6.79-6.65(m,3H),2.58-2.32(m,2H),2.04-1.69(m,4H),1.69-1.46(m,4H),1.45-1.26(m,16H).
EXAMPLE 4 Synthesis of Compound CPD017
Synthesis of Compound CPD017
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD017 (14.21 g, purity: 99.93%, yield: 76.06%) was obtained as the objective compound. Sublimation purification of 14.21g of crude CPD017 gave sublimated pure CPD017 (10.13 g, purity: 99.94%, yield: 71.28%), mass Spectrometry: 854.26 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.69(d,J＝7.5Hz,1H),7.57-7.48(m,5H),7.30-6.86(m,18H),6.62-6.57(m,4H),6.42(s,1H),1.98(m,4H),1.73-1.26(m,22H).
EXAMPLE 5 Synthesis of Compound CPD029
Synthesis of Compound CPD029-2
The synthesis and purification method of the reference compound CPD003-3 only needs to change the corresponding original material to obtain the target compound CPD029-2 (20.87 g, purity: 99.88%, yield: 74.41%), mass spectrum: 402.22 (M+H).
Synthesis of Compound CPD029
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD029 (17.86 g, purity: 99.91%, yield: 70.11%) was obtained as the objective compound. Sublimation purification of 17.86g of crude CPD029 gave sublimated pure CPD029 (14.55 g, purity: 99.92%, yield: 81.46%), mass spectrum: 828.14 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.70-7.65(m,1H),7.51-7.44(m,3H),7.44-7.36(m,3H),7.23(d,J＝3.1Hz,2H),7.13-7.05(m,3H),7.03-6.87(m,8H),6.86-6.78(m,3H),6.78-6.68(m,4H),6.63-6.59(m,1H),2.34(s,3H),1.88-1.74(m,4H),1.63-1.58(m,4H),1.27(s,18H).
EXAMPLE 6 Synthesis of Compound CPD038
Synthesis of Compound CPD038-2
The synthesis and purification method of the reference compound CPD003-3 only needs to change the corresponding original material to obtain the target compound CPD038-2 (20.87 g, purity: 99.73%, yield: 70.51%), mass spectrum: 428.23 (M+H).
Synthesis of Compound CPD038
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid was obtained as the objective compound CPD038 (14.16 g, purity: 99.92%, yield: 70.01%). Sublimation purification of 14.16g crude CPD038 gave sublimated pure CPD038 (11.03 g, purity: 99.93%, yield: 77.89%), mass Spectrometry: 878.26 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.62(m,8H),7.41(d,J＝2.9Hz,2H),7.36-7.21(m,6H),7.18-7.08(m,4H),7.08-6.94(m,7H),2.56(s,2H),2.24-1.68(m,8H),1.64-1.32(m,16H),1.00(s,6H).
EXAMPLE 7 Synthesis of Compound CPD048
Synthesis of Compound CPD048
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and thus, CPD048 (20.55 g, purity: 99.94%, yield: 77.41%) was obtained as a white solid as the objective compound. Sublimation purification of 20.55g of crude CPD048 gave sublimated pure CPD048 (14.58 g, purity: 99.94%, yield: 70.94%), mass Spectrometry: 856.16 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.66(m,1H),7.53-7.45(m,3H),7.45-7.37(m,3H),7.21(s,2H),7.11-6.88(m,13H),6.88-6.62(m,7H),1.73-1.54(m,9H),1.49-1.36(m,5H)1.12(s,18H).
EXAMPLE 8 Synthesis of Compound CPD050
Synthesis of Compound CPD050
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid was obtained as the target compound CPD050 (17.63 g, purity: 99.91%, yield: 69.83%). Sublimation purification of 17.63g of crude CPD050 gave sublimated pure CPD050 (13.03 g, purity: 99.93%, yield: 73.90%), mass Spectrometry: 828.46 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.73-7.64(m,1H),7.51(d,J＝3.2Hz,1H),7.49-7.37(m,4H),7.25-7.14(m,4H),7.07-6.89(m,10H),6.89-6.60(m,9H),1.74-1.53(m,2H),1.48-1.46(m,3H),1.41-1.36(m,5H),1.20(s,18H).
EXAMPLE 9 Synthesis of Compound CPD059
Synthesis of Compound CPD059-2
The synthesis and purification method of the reference compound CPD003-3 only needs to change the corresponding original material to obtain the target compound CPD059-2 (18.01 g, purity: 99.59%, yield: 80.00%), mass spectrum: 484.22 (M+H).
Synthesis of Compound CPD059
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD059 (17.56 g, purity: 99.91%, yield: 79.77%) was obtained as the objective compound. Sublimation purification of 17.56g of crude CPD059 gave sublimated pure CPD059 (12.97 g, purity: 99.93%, yield: 73.86%), mass spectrum: 910.23 (M+H).
1 H NMR(400MHz,CDCl 3 )7.71-7.64(m,1H),7.52-7.44(m,3H),7.44-7.36(m,3H),7.25(d,J＝2.9Hz,2H),7.18-7.07(m,6H),7.06-6.88(m,8H),6.88-6.78(m,3H),6.78-6.64(m,2H),2.53-2.50(m,1H),1.71-1.49(m,10H),1.49-1.38(m,10H),1.22(s,18H).
EXAMPLE 10 Synthesis of Compound CPD071
Synthesis of Compound CPD071-2
The synthesis and purification method of the reference compound CPD003-3 only needs to change the corresponding original material to obtain the target compound CPD071-2 (17.77 g, purity: 99.81%, yield: 80.20%), mass spectrum: 491.20 (M+H).
Synthesis of Compound CPD071
The synthesis and purification method of the reference compound CPD003 were carried out by changing the corresponding starting materials, and white solid CPD071 (16.58 g, purity: 99.92%, yield: 77.63%) was obtained as the objective compound. Sublimation purification of 16.58g crude CPD071 gave sublimated pure CPD071 (11.58 g, purity: 99.93%, yield: 69.84%), mass spectrum: 917.42 (M+H).
1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝7.7Hz,2H),7.72(d,J＝3.3Hz,1H),7.43-7.39(m,2H),7.39-7.30(m,3H),7.20(d,J＝3.1Hz,2H),7.19-6.95(m,11H),6.94-6.84(m,4H),6.82-6.71(m,5H),6.70-6.62(m,2H),1.71-1.56(m,4H),1.47-1.40(m,6H),1.20(s,18H).
EXAMPLE 11 Synthesis of Compound CPD075
Synthesis of Compound CPD075-2
Compound CPD003-4 (20.00 g,39.41 mmol), CPD075-1 (6.78 g,43.35 mmol), dichloro-di-tert-butyl- (4-dimethylaminophenyl) palladium (II) (0.56 g,0.79 mmol), potassium carbonate (10.89 g,78.82 mmol), tetrahydrofuran (300 ml), deionized water (100 ml) were added to a 1000ml three-necked round bottom flask, nitrogen was replaced three times, and the temperature was raised to 65℃for 4 hours. TLC (ethyl acetate: n-hexane=1:20 as developing solvent) was used up to monitor the consumption of starting material CPD 003-4.
Cooling to 50deg.C, concentrating under reduced pressure to remove tetrahydrofuran, adding ethyl acetate (800 ml), washing with deionized water (3×350 ml), separating, purifying by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane=1:30 as eluent), eluting, concentrating under reduced pressure at 60deg.C to obtain white solid CPD075-2 (16.75 g, purity: 99.61%, yield: 78.85%), and mass spectrometry: 539.12 (M+H).
Synthesis of Compound CPD075
The synthesis and purification method of the reference compound CPD003 only need to change the corresponding original material, the reaction solvent is dimethylbenzene, and the reaction is carried out for 5 hours at 130 ℃ to obtain a white solid which is the target compound CPD075 (13.05 g, purity: 99.94%, yield: 74.22%). Sublimation purification of 13.05g of crude CPD075 gave sublimated pure CPD075 (10.01 g, purity: 99.94%, yield: 76.70%), mass Spectrometry: 890.20 (M+H).
1 H NMR(400MHz,CDCl 3 )δ7.72 -7.67(m,2H),7.58(d,J＝2.9Hz,1H),7.54-7.44(m,3H),7.43-7.34(m,3H),7.21(d,J＝3.1Hz,2H),7.19-7.11(m,2H),7.07-6.89(m,10H),6.89-6.71(m,8H),6.68-6.66(m,2H),1.82-1.75(m,2H),1.68-1.60(m,2H),1.49-1.41(m,4H),1.21(s,18H).
Application example: fabrication of organic electroluminescent device
50mm 1.0mm glass substrate with ITO (100 nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees and then subjected to N2 Plasma treatment for 30 minutes. The washed glass substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus, and first, a compound HATCN was deposited on the surface of the transparent electrode line so as to cover the transparent electrode line, to form a thin film having a film thickness of 5nm, then, a thin film having a film thickness of 60nm was deposited as HTL1, and then, a thin film having a film thickness of 10nm was deposited as HTL2 on the HTM1 thin film, and then, a host material and a dopant material (the ratio of 98%: 2%) were deposited on the HTM2 thin film in a co-vapor deposition mode, and the film thickness of 25nm. And then, sequentially carrying out collocation evaporation of HBL (5 nm) serving as a hole blocking layer material and ETL (30 nm) serving as an electron transport material on the light-emitting layer according to the following table, then, carrying out evaporation of LiQ (1 nm) serving as an electron injection material on the electron transport material layer, and then, carrying out co-evaporation of Mg/Ag (100 nm, 1:9) serving as a cathode material.
Evaluation:
the above devices were subjected to device performance testing, and the compounds of examples of the present invention and comparative examples 1 to 3 were compared as HTL layers, respectively, using a constant current power supply (Keithley 2400), using a constant current density flowing through the light emitting element, and using spectroscopic radiation both (CS 2000) to test the luminescence spectrum. At the same time, the current density is 20mA/cm 2 Next, the device voltage value, current efficiency, and the time for which the test luminance was 90% of the initial luminance were measured (LT 90). The results are shown in Table 1 below:
sublimation temperature contrast: the sublimation temperature is defined as: the vapor deposition rate was 1 angstrom per second at a vacuum of 10-7 Torr. The test results were as follows:
| material | Sublimation temperature/. Degree.C |
| CPD003 | 264 |
| CPD014 | 263 |
| CPD017 | 266 |
| CPD029 | 265 |
| CPD050 | 267 |
| Comparative Compound 1 | 268 |
| Comparative Compound 2 | 268 |
| Comparative Compound 3 | 265 |
| Comparative Compound 4 | 275 |
| HTM1 | 380 |
| HTM2 | 275 |
As can be seen from the comparison of the data in the table above, the hole transport material of the present invention has a lower sublimation temperature, which is advantageous for industrial application.
Carrier lateral mobility contrast:
modifying 50mm 1.0mm glass substrate into transparent ITO (100 nm) electrode and Mg/Ag (100 nm, 1:9) cathode material at two ends, carrying 5mm 0.4mm groove in the middle, ultrasonically cleaning in ethanol for 10 min, oven drying at 150 deg. and passing through N 2 Plasma treatment for 30 minutes. Mounting the washed glass substrate onOn a substrate holder of a vacuum vapor deposition apparatus, first, an HTL1 layer (3% HATCN was doped to CPD014, CPD017, comparative 1-3 compound, HTM 1) having a film thickness of 10nm was deposited on a surface on the side where a transparent electrode was present so as to cover the transparent electrode, then an HTL2 layer (CPD 014, CPD017, comparative 1-3 compound, HTM 1) having a film thickness of 100nm was deposited, and after packaging, the voltage-current curve was measured to obtain transverse transmission current data, and the transverse resistance value ratio of each material (calculated by taking comparative compound 1 as 100%) was calculated. It can be observed that when the test voltage is 15v, the transverse resistance values of CPD014 and CPD017 are higher than those of the comparative compounds 1-3 and HTM1, which indicates that the carrier has small transverse mobility and small transverse crosstalk current, and is beneficial to better low gray scale color purity.
| HTL1 | HTL2 | Transverse resistance ratio (%) |
| 3％HATCN：97％CPD014 | CPD014 | 355％ |
| 3％HATCN：97％CPD017 | CPD017 | 271％ |
| 3% hatcn:97% comparative 1 | Comparative 1 | 100％ |
| 3% hatcn:97% comparative 2 | Comparative example 2 | 97％ |
| 3% hatcn:97% comparative 3 | Comparative example 3 | 99％ |
| 3% hatcn:97% comparative 4 | Comparative example 4 | 95％ |
| 3％HATCN：97％HTM1 | HTM1 | 69％ |
The material has the advantages of high light and electricity stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of the device and the like, and can be used in an organic electroluminescent device. In particular, as a hole injection/transport material, there is a possibility of application to the AMOLED industry.
Claims (4)
1. A spiro compound having one of the structures represented by formulas (6) - (9):
wherein ring a of the spiro compound is one of the following aliphatic rings:
wherein Ar is selected from substituted or unsubstituted biphenyl, fluorenyl or carbazolyl,
wherein the R is 1 ，R 2 Is unsubstituted C1-C10 alkyl; and R is 1 And R is R 2 Similarly, the substitution is by deuterium, F, cl, br, C1-C6 alkyl.
2. A spiro compound is one of the following structural formulas,
3. use of the spiro compound according to any one of claims 1-2 in an organic electroluminescent device.
4. Use according to claim 3, as hole injection layer and/or hole transport layer for organic electroluminescent devices, of the spiro compound according to any one of claims 1 to 2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310041395 | 2023-01-12 | ||
| CN2023100413959 | 2023-01-12 |
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