CN112812123A - Hole compound, preparation method thereof and organic electroluminescent device - Google Patents
Hole compound, preparation method thereof and organic electroluminescent device Download PDFInfo
- Publication number
- CN112812123A CN112812123A CN202011614819.9A CN202011614819A CN112812123A CN 112812123 A CN112812123 A CN 112812123A CN 202011614819 A CN202011614819 A CN 202011614819A CN 112812123 A CN112812123 A CN 112812123A
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- Prior art keywords
- unsubstituted
- substituted
- hole
- formula
- raw material
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 238000002347 injection Methods 0.000 claims abstract description 15
- 239000007924 injection Substances 0.000 claims abstract description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 12
- 230000005525 hole transport Effects 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- 239000002994 raw material Substances 0.000 claims description 40
- 239000010410 layer Substances 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 125000001424 substituent group Chemical group 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 12
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 10
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- VRAMUZKZGCVAFP-UHFFFAOYSA-N 2-oxo-2-(2-phenylphenoxy)acetic acid Chemical compound C(C(=O)OC1=C(C=CC=C1)C1=CC=CC=C1)(=O)O VRAMUZKZGCVAFP-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- 235000011009 potassium phosphates Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- -1 nitro, hydroxyl Chemical group 0.000 claims description 4
- 239000001301 oxygen Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 64
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 239000007787 solid Substances 0.000 description 48
- 238000003756 stirring Methods 0.000 description 37
- 239000003208 petroleum Substances 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 23
- 238000001035 drying Methods 0.000 description 22
- 239000005416 organic matter Substances 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 20
- 238000002386 leaching Methods 0.000 description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000001816 cooling Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005446 dissolved organic matter Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- VKRWRNVGVPSVLA-UHFFFAOYSA-N n,n'-bis(2-phenylphenyl)oxamide Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1NC(=O)C(=O)NC1=CC=CC=C1C1=CC=CC=C1 VKRWRNVGVPSVLA-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical compound 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 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- HONWGFNQCPRRFM-UHFFFAOYSA-N 2-n-(3-methylphenyl)-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HONWGFNQCPRRFM-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
- 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 1
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 101150088517 TCTA gene Proteins 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 1
- QZXNDEONRUSYFB-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]-3-methylaniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(N)=CC=2)=C1 QZXNDEONRUSYFB-UHFFFAOYSA-N 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- 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
- H10K50/15—Hole transporting layers
-
- 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]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
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Abstract
The invention discloses a hole compound, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of chemistry and organic luminescent materials, wherein the structure general formula of the hole compound is as follows:
wherein X, Y is independently O, S, N-R3Any one of (a); ring A is any of a substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 10-membered) heteroaryl; l1, L2 are each independently at least one of a linkage, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl. The hole injection layer and/or the device prepared by the hole compoundOr a hole transport layer, can improve the luminous efficiency of the device, reduce the driving voltage of the device, and thus can enhance the durability of the resulting organic electroluminescent device.
Description
Technical Field
The invention relates to the technical field of chemistry and organic light-emitting materials, in particular to a hole compound, a preparation method thereof and an organic electroluminescent device.
Background
The OLED is a hole and electron dual injection type light emitting device, and directly converts electric energy into light energy of organic semiconductor material molecules. Compared with traditional display devices such as a CRT (cathode ray tube), an LCD (liquid crystal display), a PDP (plasma display panel) and the like, the OLED has all the advantages of the existing display, has unique advantages, not only has high brightness, high contrast, high definition, wide visual angle, wide color gamut and the like to realize high-quality images, but also has the characteristics of ultra-thinness, ultra-lightness, low driving voltage, low power consumption, wide temperature and the like to meet the requirements of portable equipment on portability, power saving and outdoor operation; the OLED display has the unique characteristics of self-luminescence, high luminous efficiency, short response time, transparency, flexibility and the like.
The research on the hole-type material mainly focuses on the arylamine-type compound. The arylamine compound has high hole mobility and is an ideal hole transport material. The focus of the research at present is mainly to improve the thermal stability of the compounds and the stability of the film form of the compounds. Commonly used small molecule hole-blocking materials are mainly 1, 1-bis [4- [ N, N-di (p-tolylene) amino ] phenyl ] cyclohexane (TAPC), tris (4-carbazol-9-ylphenyl) amine (TcTa), N, N, N ', N' -Tetraphenylbenzidine (TPB), n, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1 ' -biphenyl-4, 4' -diamine (α -NPD), N ' -diphenyl-N, N ' - (3-methylphenyl) -1,1 ' -biphenyl-4, 4' -diamine (TPD), 4',4 ″ -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), and the like.
However, in organic electroluminescent devices using these materials, whether for fluorescent OLEDs or phosphorescent OLEDs, further improvements are still required in terms of luminous efficiency, lifetime, operating voltage, and the like.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a hole-based compound to solve the problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a cavity compound has a structural general formula as shown in formula I:
in the formula, m and n are both natural numbers and are not zero at the same time; x, Y is independently O, S, N-R3Any one of (a);
R1、R2、R3each independently is at least one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
ring A is any of a substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 10-membered) heteroaryl;
l1, L2 are each independently at least one of a linkage, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl;
Ar1、Ar2、Ar3、Ar4each independently at least one of substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, C1-C30 alkoxy, C6-C60 aryloxy, C3-C30 aliphatic ring linked to an adjacent substituent to form a mono-or polycyclic ring, or 3-to 30-membered aromatic ring.
Preferably, the carbon atom in the C3-C30 aliphatic ring or the 3 to 30 membered aromatic ring, which is linked to an adjacent substituent to form a mono-or polycyclic ring, is replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur.
Preferably, X, Y are both O.
Preferably, the heteroatoms in the heterocycloalkyl, heteroaryl and heteroarylamino groups are independently at least one of oxygen, nitrogen and sulfur.
Preferably, the chemical structural formula of the hole-like compound is any one of formula H01-formula H48:
in the present specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are connected, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
Heterocyclyl is meant to include both aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl and the like, and cyclic ethers/thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene and the like. In addition, the heterocyclic group may be optionally substituted.
Another object of an embodiment of the present invention is to provide a method for preparing the above hole-based compound, which includes the following steps:
under the protective atmosphere, placing the raw material A and the raw material B in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate 1;
under the protective atmosphere, placing the raw material C and the raw material D in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate 2;
under the protective atmosphere, putting the intermediate 1 and the intermediate 2 into Dimethylformamide (DMF), and adding potassium phosphate, N' -bis (2-phenylphenyl) oxalic acid and cuprous iodide to react to obtain an intermediate 3;
under the protective atmosphere, dissolving the intermediate 3 in a tetrahydrofuran solution, and then dropwise adding the tetrahydrofuran solution of n-BuLi and the raw material E for reaction to obtain an intermediate 4;
under the protective atmosphere, adding glacial acetic acid into the intermediate 4, dropwise adding concentrated sulfuric acid to react, and then adding a sodium bicarbonate solution to terminate the reaction to obtain the hole compound;
the structural formula of the raw material A is shown as a formula A, the structural formula of the raw material B is shown as a formula B, the structural formula of the raw material C is shown as a formula C, the structural formula of the raw material D is shown as a formula D, and the structural formula of the raw material E is shown as a formula E:
preferably, the solvent is a mixture of toluene, ethanol and water.
Specifically, the synthetic route of the preparation method is as follows:
the method specifically comprises the following steps:
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, raw material A (1.0eq) and raw material B (1.0eq) were dissolved in toluol and water (V)tol:VToluene:VWater (W)Adding palladium tetratriphenylphosphine (0.01eq) and potassium carbonate (2.0eq) into the mixed solution of (3: 1:1), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 1;
step two: preparation of intermediate 2
Under the protection of nitrogen, raw material C (1.0eq) and raw material D (1.0eq) were dissolved in toluol and water (V)tol:VToluene:VWater (W)Adding palladium tetratriphenylphosphine (0.01eq) and potassium carbonate (2.0eq) into the mixed solution of (3: 1:1), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 2;
step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(1.0eq) and the intermediate 2(1.0eq) in an anhydrous DMF (0.4eq) solution, adding dry potassium phosphate (2.0eq), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.02eq) and cuprous iodide (CuI) (0.02eq), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, slowly dropping the solution into water after the solution is cooled to room temperature, stirring for 1 hour, standing the solution, precipitating out, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3;
step four: preparation of intermediate 4
Adding the intermediate 3(1.0eq) into a three-neck flask under the protection of nitrogen, adding anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (1.2eq), and stirring for 2 hours at-78 ℃. Dissolving a raw material E (1.0eq) in a tetrahydrofuran solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying to prepare an intermediate 4;
step five: preparation of chemical formula 1
Adding the intermediate 4(1.0eq) into a three-neck flask, adding glacial acetic acid (10eq), heating to 120 ℃, adding concentrated sulfuric acid (0.1eq) dropwise, and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the water phase with dichloromethane for three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, drying, and preparing the hole compound shown in the chemical formula 1.
Another object of the embodiments of the present invention is to provide an application of the hole-based compound in the preparation of organic electroluminescent devices.
It is another object of an embodiment of the present invention to provide an organic electroluminescent device, which includes an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes the hole-based compound.
Preferably, the organic layer includes a hole injection layer and/or a hole transport layer; the hole injection layer and/or the hole transport layer partially or completely contain the hole-based compound.
Specifically, the above-mentioned organic layer may be formed in a single layer structure, but may also be formed in a multilayer structure in which a layer and two or more organic material layers are formed. For example, the organic layer may have a structure including a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.
The kind of the anode is not particularly limited, and may be a conventional anode known to those skilled in the art, and is more preferably one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide. The thickness of the anode is preferably set to
The kind of the cathode is not particularly limited, and may be a conventional cathode well known to those skilled in the art, and more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb.
The cathode preferably has a thickness
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the host material can be 4,4'-N, N' -dicarbaOxazole-biphenyl ("CBP"), and the like; the doping material can be Ir (ppy)3And the like iridium complexes.
The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art. Preferably: the electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transport layer is preferably
The electron injection layer is LiF, CsF, Li2O、Al2O3MgO; the thickness of the electron injection layer is preferably 0.1 to 10 nm.
In the embodiment of the present invention, the various functional layers described above may be formed by a solution coating method and a vacuum deposition method. The solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, etc., but is not limited thereto.
The organic electroluminescent device can be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), or the like, according to the same principle, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the hole compound provided by the embodiment of the invention, the benzo-heterocycle rigid structure is introduced, so that the hole compound has good film-forming property and thermal stability. In addition, the hole-based compound of the present invention has high hole injection and movement rates; therefore, the hole injection layer and/or the hole transport layer of the organic electroluminescent device prepared by using the hole compound can improve the luminous efficiency of the device, reduce the driving voltage of the device and further enhance the durability of the obtained organic electroluminescent device.
Detailed Description
The following are examples of the present invention, which are provided to aid understanding of the present invention and are not intended to limit the scope of the present invention. In addition, the preparation methods of the compounds which are not specifically listed in the embodiments of the present invention are methods generally applied in the related industries, and the methods described in the embodiments can be referred to when preparing other compounds.
Example 1
This example provides a hole-like compound, which is prepared by the following method:
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1(16.65g, the yield is 83.2%, and the MW: 400.31).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(11.52g, the yield is 92.5%, and the MW: 249.15).
Step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the intermediate 2(30mmol) in an anhydrous DMF (12mmol) solution, adding dry potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dripping the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(13.90g, the yield is 81.5%, and the MW: 568.53).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(10.48g, yield 78.9%, MW: 663.85).
Step five: preparation of formula H01
Adding the intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid, heating to 120 ℃, dropwise adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the hole-like compound shown as chemical formula H01 (7.19g, yield of 74.2%, MW: 645.83).
Example 2
This example provides a hole-like compound, which is prepared by the following method:
the method comprises the following steps: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(23.58g, the yield is 91.3%, and the MW: 516.45).
Step two: preparation of intermediate 3
Under the protection of nitrogen, dissolving raw material 1(35mmol) and intermediate 2(30mmol) in anhydrous DMF (12mmol), adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropping the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (2) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(15.03g, the yield is 82.3%, and the MW: 608.50).
Step three: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(12.35g, 79.4% yield, MW: 777.93).
Step four: preparation of formula H04
Adding the intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid, heating to 120 ℃, dropwise adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the hole-like compound shown as chemical formula H04 (8.41g, yield 73.8%, MW: 759.96).
Example 3
This example provides a hole-like compound, which is prepared by the following method:
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organic matter is completely dissolved by using 30mL of dichloromethane, then slowly dropped into the petroleum ether solution, stirred uniformly, precipitated, filtered to obtain a solid, and sequentially leached by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether and dried to obtain an intermediate 1(16.53g, the yield is 82.4 percent, and the MW: 401.33).
Step two: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the raw material 2(35mmol) in an anhydrous DMF (12mmol) solution, adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropping the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(12.09g, the yield is 81.7%, and the MW: 493.45).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(11.92g, 77.9% yield, MW: 764.83).
Step five: preparation of formula H22
Adding the intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid, heating to 120 ℃, dropwise adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the hole-like compound shown as chemical formula H22 (8.27g, yield 73.8%, MW: 746.88).
Examples 4 to 8
Because the synthetic routes and principles of the preparation methods of other hole-pair compounds having the structural general formula of formula I in the disclosure are the same as those of the above-listed examples 1 to 3, the raw materials are only required to be replaced with the raw materials corresponding to the corresponding ligand structures in the target product, and the corresponding hole-pair compounds can be obtained by adjusting the material amounts according to the corresponding stoichiometric ratios, so that the examples are not exhaustive, the synthesis of the hole-pair compounds H18, H28, H35, H42 and H45 is completed with reference to the preparation methods of examples 1 to 3, and the mass spectra and the molecular formulae of the hole-pair compounds are shown in table 1.
TABLE 1
| Examples | Compound (I) | Molecular formula | Theoretical value of mass spectrum | Mass spectrometric test values |
| Example 4 | H18 | C41H33NO2 | 571.72 | 571.75 |
| Example 5 | H28 | C58H42N2O2 | 798.99 | 798.98 |
| Example 6 | H35 | C46H32N2O2 | 644.77 | 644.75 |
| Example 7 | H42 | C49H34N2O2 | 682.82 | 682.84 |
| Example 8 | H44 | C50H34N4O2 | 722.85 | 722.87 |
Device example 1
The embodiment of the device provides an organic electroluminescent device, and the specific preparation method comprises the following steps:
firstly, N1- (naphthalene-2-yl) -N4, N4-di (4- (naphthalene-2-yl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine ("2-TNATA") is evaporated on an ITO (anode) to a thickness of 50nm, and then the hole-type compound H01 is evaporated to a thickness of 40nm to form a hole transport layer, a host substance of 4,4'-N, N' -dicarbazole-biphenyl ("CBP") and a doping substance of tris (2-phenylpyridine) iridium ("Ir (ppy)3") according to 95: 5 weight ratio, 30nm of thickness is mixed evaporation for forming a luminescent layer, 10nm of thickness is mixed evaporation for forming a hole blocking layer ('BALq'), 35nm of thickness is mixed evaporation for forming an electron transport layer, 0.2nm of thickness is mixed evaporation for forming an electron injection layer LiF, and 120nm of thickness is mixed evaporation for forming a cathode Al, and the organic electroluminescent device is formed.
Device example 2-device example 8
With reference to the preparation method provided in device example 1 above, the hole-based compound H01 used in device example 1 was replaced with the hole-based compounds H04, H18, H22, H35, H42, and H44 provided in the above examples, respectively, as hole transport layer materials, and the corresponding organic electroluminescent devices were prepared.
Comparative device example 1
The device comparative example produced an organic electroluminescent device. Specifically, the hole-based compound H01 used in device example 1 was replaced with the comparative compound NPB as a hole transport layer material, and a corresponding organic electroluminescent device was prepared. Wherein the structural formula of NPB is as follows:
the driving voltage, the light emitting efficiency, and the lifetime of the organic electroluminescent devices obtained in the device examples 1 to 8 and the device comparative example 1 were characterized at 6000(nits) luminance, and the results of the characterization are shown in table 2 below.
TABLE 2
The results in table 2 show that the hole-based compound provided by the invention can be applied to an organic electroluminescent device, and compared with the hole transport layer material NPB, the organic electroluminescent device provided by the invention has lower starting voltage, and the luminous efficiency and the service life are remarkably improved.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The cavity compound is characterized in that the structural general formula of the cavity compound is shown as formula I:
in the formula, m and n are both natural numbers and are not zero at the same time; x, Y is independently O, S, N-R3Any one of (a);
R1、R2、R3each independently is at least one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
ring A is any of a substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 10-membered) heteroaryl;
l1, L2 are each independently at least one of a linkage, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl;
Ar1、Ar2、Ar3、Ar4each independently at least one of substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, C1-C30 alkoxy, C6-C60 aryloxy, C3-C30 aliphatic ring linked to an adjacent substituent to form a mono-or polycyclic ring, or 3-to 30-membered aromatic ring.
2. The cavityless compound of claim 1, wherein the carbon atom in the C3-C30 aliphatic or 3-to 30-membered aromatic ring linked to an adjacent substituent to form a mono-or polycyclic ring is replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur.
3. The cavitated compound of claim 1, wherein X, Y is O.
4. The cavitated compound of claim 3, wherein the heteroatoms in the heterocycloalkyl, heteroaryl, and heteroarylamino groups are independently at least one of oxygen, nitrogen, and sulfur.
5. The hole-based compound of claim 1, wherein the chemical structural formula of the hole-based compound is any one of formula H01-formula H48:
6. a method for preparing the hole-like compound according to any one of claims 1 to 5, comprising the steps of:
under the protective atmosphere, placing the raw material A and the raw material B in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate 1;
under the protective atmosphere, placing the raw material C and the raw material D in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate 2;
under the protective atmosphere, putting the intermediate 1 and the intermediate 2 into dimethylformamide, and adding potassium phosphate, N' -bis (2-phenylphenyl) oxalic acid and cuprous iodide to react to obtain an intermediate 3;
under the protective atmosphere, dissolving the intermediate 3 in a tetrahydrofuran solution, and then dropwise adding the tetrahydrofuran solution of n-BuLi and the raw material E for reaction to obtain an intermediate 4;
under the protective atmosphere, adding glacial acetic acid into the intermediate 4, dropwise adding concentrated sulfuric acid to react, and then adding a sodium bicarbonate solution to terminate the reaction to obtain the hole compound;
the structural formula of the raw material A is shown as a formula A, the structural formula of the raw material B is shown as a formula B, the structural formula of the raw material C is shown as a formula C, the structural formula of the raw material D is shown as a formula D, and the structural formula of the raw material E is shown as a formula E:
7. the method for producing a hole-based compound according to claim 6, wherein the solvent is a mixed solution of toluene, ethanol, and water.
8. An organic electroluminescent device comprising an anode, a cathode and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the hole-based compound according to any one of claims 1 to 5.
9. An organic electroluminescent device according to claim 8, wherein the organic layer comprises a hole injection layer and/or a hole transport layer; the hole injection layer and/or the hole transport layer partially or completely contain the hole-based compound.
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| CN115160322A (en) * | 2022-05-07 | 2022-10-11 | 吉林奥来德光电材料股份有限公司 | Hole organic electroluminescent compound and preparation method thereof |
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