CN114075131A - TADF material, preparation method thereof and organic electroluminescent device thereof - Google Patents
TADF material, preparation method thereof and organic electroluminescent device thereof Download PDFInfo
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- CN114075131A CN114075131A CN202110008869.0A CN202110008869A CN114075131A CN 114075131 A CN114075131 A CN 114075131A CN 202110008869 A CN202110008869 A CN 202110008869A CN 114075131 A CN114075131 A CN 114075131A
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- 239000000463 material Substances 0.000 title claims abstract description 270
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 125000001424 substituent group Chemical class 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 45
- 150000002367 halogens Chemical class 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 28
- -1 9-carbazolyl Chemical group 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 26
- 230000005525 hole transport Effects 0.000 claims description 25
- 238000012546 transfer Methods 0.000 claims description 22
- 125000002252 acyl group Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000004414 alkyl thio group Chemical group 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 10
- 125000004986 diarylamino group Chemical group 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 150000004756 silanes Chemical class 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical class 0.000 claims description 5
- 125000000041 C6-C10 aryl group Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 150000001975 deuterium Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 84
- 238000012795 verification Methods 0.000 description 49
- 125000004432 carbon atom Chemical group C* 0.000 description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 150000001555 benzenes Chemical group 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- YKYMGFVDWOIHJH-UHFFFAOYSA-N (4-cyano-3,5-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC(F)=C(C#N)C(F)=C1 YKYMGFVDWOIHJH-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000005620 boronic acid group Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 125000005017 substituted alkenyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 1
- MEGGHYWNWKHTDW-UHFFFAOYSA-N 2,4-dibromothiophene-3-carbonitrile Chemical compound BrC1=CSC(Br)=C1C#N MEGGHYWNWKHTDW-UHFFFAOYSA-N 0.000 description 1
- CQXZSEXZQVKCHW-UHFFFAOYSA-N 3,5-difluorobenzonitrile Chemical compound FC1=CC(F)=CC(C#N)=C1 CQXZSEXZQVKCHW-UHFFFAOYSA-N 0.000 description 1
- YQKMWXHJSIEAEX-UHFFFAOYSA-N 3,6-dimethoxy-9H-carbazole Chemical compound C1=C(OC)C=C2C3=CC(OC)=CC=C3NC2=C1 YQKMWXHJSIEAEX-UHFFFAOYSA-N 0.000 description 1
- TZHQWUAOIWRFSW-UHFFFAOYSA-N 4-bromo-2,6-difluorobenzonitrile Chemical compound FC1=CC(Br)=CC(F)=C1C#N TZHQWUAOIWRFSW-UHFFFAOYSA-N 0.000 description 1
- ZXMDULRSHHXKIU-UHFFFAOYSA-N 6-chloro-n-(2,4-dimethoxyphenyl)-1-(4-methoxyphenyl)-1,3,4,9-tetrahydropyrido[3,4-b]indole-2-carboxamide Chemical compound C1=CC(OC)=CC=C1C1C(NC=2C3=CC(Cl)=CC=2)=C3CCN1C(=O)NC1=CC=C(OC)C=C1OC ZXMDULRSHHXKIU-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 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 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of luminescent materials, in particular to a TADF material, a preparation method thereof and an organic electroluminescent device thereof. The TADF material is a compound with any structural formula in the following general formula or a tautomer thereof,
and
wherein X 'represents a substitution at an arbitrary position on the benzene ring, and X' is C, Si or N and when it is N, the corresponding group is not linked, X ″ is selected from any one of O, S, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group and a substituted silane group; r1‑R6At least one of them is a group of the general formula (a),
X1‑X8each independently selected from C or N, R21‑R28Each independently selected from hydrogen, deuterated hydrogen, or a substituent. The TADF material has a proper triplet state energy level and can be used as a sensitizer of a light-emitting layer.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a TADF material, a preparation method thereof and an organic electroluminescent device thereof.
Background
A Thermally Activated Delayed Fluorescence (TADF) material based on a triplet-to-singlet transition found by the Adachi research group of kyushu university in japan is a novel material that realizes reverse intersystem crossing of energy from a triplet excited state to a singlet excited state using ambient heat, and can realize high luminous efficiency without using expensive rare metals. The TADF material serving as a sensitized fluorescent emitter is different from a common fluorescent material and a traditional TADF material, combines the traditional fluorescent material and the TADF material, and realizes the preparation of the organic fluorescent OLED with high conversion efficiency, high color purity and low cost by utilizing the energy collecting capability of the TADF material and the high-purity light color of the traditional fluorescent material. Compared to pure TADF-luminescent materials, TADF sensitizer materials have higher emission efficiency, high singlet energy levels and high stability. When the TADF-sensitized fluorescent device and the traditional fluorescent material are used as a light emitter, the TADF-sensitized fluorescent device and the traditional fluorescent material are only required to be used as a doping body, a main material and a fluorescence emitter material to be evaporated together to form a luminescent layer, when electron holes are compounded into excitons in the main body, the excitons firstly transfer energy to the TADF material, transfer electrons on a triplet state to a singlet state through the anti-system crossing capability of the TADF material, then the TADF material transfers the singlet state energy to the traditional fluorescent material completely (known as FRET process), and finally the traditional fluorescent material emits fluorescence, which is also known as super fluorescence. The TADF material need not itself emit light during the entire process, but rather serves to collect energy and transfer it to the fluorescence emitter material. Because the sensitized fluorescence is emitted by the traditional fluorescent material, the spectrum of the sensitized fluorescent emitter has the advantages of narrow spectrum and long service life of common fluorescence, and the TADF has high efficiency, so that the fluorescent emitter is suitable for the field of OLED display. Therefore, the above requirements of the conventional TADF material still have room for improvement, and there is a need to develop a new sensitized fluorescent OLED material.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a TADF material, a preparation method thereof and an organic electroluminescent device thereof. The TADF material has a proper triplet state energy level and can be used as a sensitizer of a light-emitting layer, and then energy is effectively transferred to fluorescent molecules for light emission, so that light emission is realized, energy collection and light emission are separated in the process, and excellent device performance is obtained.
The invention is realized by the following steps:
in a first aspect, the present invention provides a TADF material which is a compound having any one of the following general formulae (1) or a tautomer thereof:
wherein X 'represents a substitution at an arbitrary position on the benzene ring, and X' is C, Si or N and when it is N, the corresponding group is not linked, X ″ is selected from any one of O, S, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group and a substituted silane group; r1-R6At least one of them being a group of the formula (a), the remainder being R1-R6Each independently selected from any one of hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane and substituted or unsubstituted cycloalkyl;
and the general formula (a) satisfies at least one of the following conditions: (a) r25And R26Together form a single bond; (b) r27And R28Represent the atomic groups required to form together a substituted or unsubstituted benzene ring.
In a second aspect, the present invention provides a method for producing a TADF material according to any one of the preceding embodiments, comprising: selecting any one of the following compound raw materials and the compound containing R1-R5To obtain the TADF material;
wherein Ra-Re are independently selected from the group consisting of1-R5And reacting to obtain the group of said TADF material.
In a third aspect, the present invention provides a super luminescent material for preparing a luminescent layer, which comprises the TADF material according to any one of the previous embodiments;
preferably, it further comprises a luminescent material;
preferably, it comprises 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material;
more preferably, it comprises 20 to 40 parts by weight of the TADF material, 0.3 to 5 parts by weight of the luminescent material;
more preferably, it further comprises a host material;
more preferably, the triplet energy level and the singlet energy level of the host material are higher than the triplet energy level and the singlet energy level of the TADF material, respectively, and the triplet energy level and the singlet energy level of the TADF material are higher than the triplet energy level and the singlet energy level of the light-emitting material, respectively.
In a fourth aspect, the present invention provides a transfer material for use in the preparation of a transfer layer, comprising a TADF material according to any of the preceding embodiments;
preferably, it further comprises an electron transport material;
preferably, the lowest unoccupied rail of the electron transport material is lower than the lowest unoccupied rail of the TADF material;
preferably, the difference between the lowest unoccupied orbital of the electron transport material and the lowest unoccupied orbital of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2 eV.
In a sixth aspect, the present invention provides an organic electroluminescent device comprising at least one of the following layered structures:
(1) a light-emitting layer formed of the light-emitting material for producing a light-emitting layer described in the foregoing embodiment;
(2) a transfer layer formed of the transfer material for producing a transfer layer according to the foregoing embodiment;
preferably, the organic electroluminescent device further comprises a cathode and an anode, and at least one layer of the layered structure of (1) or (2) above is disposed between the cathode and the anode.
The invention has the following beneficial effects: (1) the TADF material provided by the embodiment of the invention takes a cyano group as an electron withdrawing group and a group shown in a general formula (a) as an electron donating group to act together, so that the charge distribution of the TADF material is adjusted, the further delocalization distribution of electrons is facilitated, the singlet state-triplet state energy level of the TADF material is adjusted, the RISC rate between energy systems is increased, the exciton concentration is reduced, and the service life of a device is prolonged.
(2) The TADF material has a proper triplet state energy level, can be used as a sensitizer of a light-emitting layer, and then effectively transfers energy to fluorescent molecules for light emission, so that narrow-spectrum light emission is realized, energy collection and light emission are separated in the process, and excellent device performance is obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Embodiments of the present invention provide a TADF material (a novel fluorescence sensitizer is also referred to as an auxiliary dopant) which is a compound having any one of the following general formulae (1) or a tautomer thereof,
The remainder of R1-R6Each independently selected from any one of hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane and substituted or unsubstituted cycloalkyl.
Specifically, when R is1-R6When one of them is a group of the formula (a), R1-R3Any one of them is a group represented by the general formula (a); in addition, R is as defined above1-R3Any one of which is a group represented by the general formula (a) is merely an example, and R4And R5A group of the formula (a) may also be selected.
When R is1-R6In the case where both are groups of the formula (a), R may be selected1And R3And is simultaneously a group of the formula (a), or R2And R4And is a group of the formula (a); r may also be selected1And R5And is simultaneously a group of the formula (a), or R1And R2And is simultaneously a group of the formula (a), or R2And R5And is simultaneously a group of the formula (a), or R3And R5And is a group represented by the general formula (a).
When R is1-R6When three of them are groups represented by the formula (a), R may be1、R3And R4And is simultaneously a group of the formula (a), or R1、R3And R5And is simultaneously a group of the formula (a), or R2、R3And R5And is simultaneously a group of the formula (a) or R2、R3And R4And is a group represented by the general formula (a).
Or has R1、R2、R3And R4Both being a group of the formula (a) and R1、R5、R3And R4And are simultaneously a group of the formula (a) or the like R1-R6In which four are exemplified by a group of the formula (a), or R1-R6Are all examples of the group represented by the general formula (a).
The above examples are all R1-R6At least one of which is a group of the formula (a), when R is not indicated1-R6The above examples of the group of which at least one is represented by the general formula (a) are only given, and other combinations of groups are also within the scope of the present invention.
Further, the group represented by the above general formula (a) is any one of the following groups: substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2, 3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl or substituted or unsubstituted diarylamino; that is to say R1-R5At least one of the substituted or unsubstituted 9-carbazolyl group, the substituted or unsubstituted 1,2, 3, 4-tetrahydro-9-carbazolyl group, the substituted or unsubstituted 1-indolyl group or the substituted or unsubstituted diarylamino group. Two, three, four or 5 of them may be selected from any one of the above groups, or a combination of a plurality of them.
More specifically, the group represented by the general formula (a) is any one of the following groups represented by the general formulae:
Further, the above R21-R28、R31-R38、R41-R46、R51-R62And R71-R80May be independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane, and substituted or unsubstituted cycloalkyl. Specifically, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl-substituted amino group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a diarylamino group having 12 to 40 carbon atoms, a substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylsulfonyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an amide group, an alkylamide group having 2 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsilylalkyl group having 4 to 20 carbon atoms, a trialkylsilylalkenyl group having 5 to 20 carbon atoms, a trialkylsilylalkyl group having 5 to 20 carbon atoms, a substituted amino group having 12 to 40 carbon atoms, a substituted or unsubstituted carbazolyl group having 12 carbon atoms, a carbon atom, Trialkylsilylkynyl having 5 to 20 carbon atoms.
Further preferably, R is as defined above21-R28、R31-R38、R41-R46、R51-R62And R71-R80Can be respectively and independently selected from hydrogen, deuterated hydrogen, hydroxyl, fluorine atom, chlorine atom, cyano, nitro, C1-10 substituted or unsubstituted alkyl, C1-10 substituted or unsubstituted alkoxy, C1-10 substituted or unsubstituted dialkylamino, C6-15 or C6-10 substituted or unsubstituted aryl, C3-12 substituted or unsubstituted heteroaryl, C12-40 substituted or unsubstituted diarylamino and C12-40 substituted or unsubstituted carbazolyl.
It is to be noted that the above-defined R is provided in the embodiments of the present invention21-R28、R31-R38、R41-R46、R51-R62And R71-R80The substituent may be an unsubstituted group, may be a groupExamples of the alkyl group having 1 to 20, 1 to 10, or 1 to 6 carbon atoms which may be substituted in one step include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, and n-butyl groups, and alkyl groups substituted with substituent groups such as halogen, hydroxyl, and nitro groups. And the alkyl group may be a straight chain or branched chain alkyl group. For example, the alkoxy group having 1 to 20 or 1 to 10 carbon atoms may be an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, or an isopropoxy group, or a substituted alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, which is substituted with a substituent such as a halogen group, a cyano group, a hydroxyl group, or a nitro group. For example, the C1-20 alkyl-substituted amino group may be CH3NH2-、(CH3)2NH-、C2H5NH2-、(C2H5)2NH-、C5H12NH2-、(C5H12)2NH-etc. CnH2n+1NH2-or (C)nH2n+1)2NH-alkyl substituted amino with 1-20 carbon atoms, wherein n is an integer, or alkyl substituted amino with 1-20 carbon atoms which is further substituted. For example, the acyl group having 2 to 20 carbon atoms may be acetyl, propionyl, hexanoyl, or the like. For example, the aryl group having 6 to 40 carbon atoms may be an unsubstituted monocyclic aryl group such as a benzene ring, a substituted monocyclic aryl group such as a benzyl group, an ortho-substituted benzene ring, a meta-substituted benzene ring, a para-substituted benzene ring, or a homotrisubstituted benzene ring (the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group, or the like), a fused unsubstituted aryl group such as anthracene or phenanthrene, a fused substituted aryl group such as substituted anthracene or phenanthrene, or a substituted or unsubstituted non-fused aryl group such as biphenyl or benzophenone. The alkenyl group having 2 to 10 carbon atoms may be an unsubstituted alkenyl group such as a vinyl group, a propenyl group, or a heptenyl group, or a substituted alkenyl group such as a halogen, an alkyl group, or a nitro group. For example, the alkynyl group having 2 to 10 carbon atoms may be an unsubstituted alkynyl group such as an ethynyl group, propynyl group or butynyl group, or an alkynyl group substituted with a halogen, an alkyl group, a nitro group or the like. The heteroaryl group having 3 to 40 carbon atoms may be a substituted or unsubstituted heteroaryl group such as pyridyl, pyridazinyl, pyrimidinyl, triazinyl, triazolyl and benzotriazolylThe heteroaryl group may be a group bonded via a heteroatom or a group bonded via a carbon atom constituting a heteroaryl ring. For example, the diarylamino group having 12 to 40 carbon atoms may be a tertiary amino group in which two benzene rings are connected or a primary amino group in which one benzene ring is connected, and the benzene ring may be further substituted, and the benzene ring may be substituted with a non-condensed aryl group such as biphenyl or a condensed aryl group such as anthracene or phenanthrene.
Further, the above R31-R38、R41-R46、R51-R62And R71-R80The selected groups may be completely different groups, may be partially identical, partially different groups, or completely identical groups. For example R31-R38、R41-R46、R51-R62And R71-R80May be all selected as H or a methyl, ethyl or chlorine atom, or may be R32And R37Selected from the same substituents as the remaining R in formula (a)31、R33-R36And R38Are all selected from a combination of different groups, R33And R36Selected from the same substituent, R34And R35Selected from the same substituent, R72And R79Selected from the same substituent, R73And R78Selected from the same substituent, R74And R77The substituents are the same, and the groups corresponding to the rest of R in the general formula (a) are different groups. Similarly, R may be72、R74、R77And R79Selected from the same substituent, while the rest in the general formula (a) are respectively different groups, or other R groups also have partial same substituent. The above examples are merely illustrative and are not meant to be the only combinations of groups described above.
Preferably, the group of formula (a) is any one of the following groups of formula:
The above substituted or unsubstituted alkyl group may be selected from the above R31-R38、R41-R46、R51-R62And R71-R80The alkyl group defined in (1) may be an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group, or an alkyl group substituted with a substituent such as a halogen group, a hydroxyl group, and a nitro group. And the alkyl group may be a straight chain or branched chain alkyl group. The substituted or unsubstituted aromatic group may be selected from the group consisting of R31-R38、R41-R46、R51-R62And R71-R80Examples of the aryl group defined in (1) include an unsubstituted monocyclic aryl group such as a benzene ring, a monocyclic aryl group substituted with a benzyl group, an ortho-substituted benzene ring, a meta-substituted benzene ring, a para-substituted benzene ring, a homotrisubstituted benzene ring and the like (wherein the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group or the like), an unsubstituted aryl group condensed with anthracene, phenanthrene or the like, and a substituted monocyclic aryl groupThe condensed aryl group such as anthracene and phenanthrene may be a substituted or unsubstituted non-condensed aryl group such as biphenyl or benzophenone. The substituted or unsubstituted amine group may be selected from CH3NH2-、(CH3)2NH-、C2H5NH2-、(C2H5)2NH-、C5H12NH2-、(C5H12)2NH-etc. CnH2n+1NH2-or (C)nH2n+1)2NH-amino substituted by C1-20 alkyl, wherein n is an integer, or amino substituted by C1-20 alkyl which is further substituted by alkyl; or a tertiary amine group connected with two benzene rings, or a primary amine group connected with one benzene ring, wherein the benzene ring can be further substituted, and the benzene ring can be replaced by non-condensed aryl such as biphenyl or condensed aryl such as anthracene and phenanthrene. The substituted silyl group may be selected from-Si (Me)3、(C2H5)3Si-、(C5H12)3Si-etc. (C)nH2n+1)3Si-, n is an integer, and the alkyl group may be a further substituted alkyl group.
More specifically, the group represented by the general formula (a) is any one of the following general formulae (1d) to (44 d):
Note that the bond with a prime symbol indicates the position of the connecting bond.
Above is to R1-R6Wherein at least one is a group represented by the general formula (a), and the remaining R is1-R6The description will be made. The method specifically comprises the following steps: the remainder of R1-R6Independently selected from hydrogen, hydroxyl, halogen, cyano, nitro, C1-C20 substituted or unsubstituted saturated alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C6-C40 substituted or unsubstituted non-heteroaromatic group, C3-C40 substituted or unsubstituted heteroaryl, C1-C20 substituted or unsubstituted alkoxy, C1-C20 substituted or unsubstituted alkylthio, -NH-, C1-C20 substituted amino, C2-C20 substituted or unsubstituted acyl, sulfonyl, C1-C10 alkyl substituted sulfonyl, amido, C67 1-C10 alkyl substituted amido, C2-C10 alkyl substituted ester, C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl, C5-C20 trialkylsilylalkyl and C3-C20 unsubstituted cycloalkyl or unsubstituted cycloalkyl Either one of them. Further preferably, the remaining R1-R5 are each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, C1-C6 saturated alkyl, C3-C10 unsubstituted cycloalkyl, C6-C20 unsubstituted fused cycloalkyl, C6-C20 substituted non-fused and non-heteroaromaticAny one of an aromatic group, a C10-C40 substituted fused non-heteroaromatic group, a C1-C10 alkyl substituted alkoxy group, a C1-C10 alkyl substituted alkylthio group, an-NH-, C1-C10 alkyl substituted amino group, a C6-C20 aryl substituted amino group, an acyl group, a sulfonyl group, a C2-C10 alkyl acyl group, a C6-C20 aryl substituted acyl group, a C1-C10 alkyl substituted sulfonyl group, an amide group, a C2-C8 alkyl substituted amide group, a C2-C8 alkyl substituted ester group, a C3-C15 trialkylsilyl group, a C4-C15 trialkylsilylalkyl group, a C5-C15 trialkylsilylalkenyl group, a C5-C15 trialkylsilylalkynyl group, and a C3-C15 substituted or unsubstituted cycloalkyl group. The remainder of R1-R5Each independently selected from any one of hydrogen, cyano, carbazolyl, diarylamino, C3-C10 alkoxy, C1-C6 alkyl and C6-C10 aryl.
It is noted that the embodiment of the present invention provides the above-defined residual R1-R6The alkyl group having 1 to 20 or 1 to 6 carbon atoms may be an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-butyl group, or an alkyl group substituted with a substituent such as a halogen, a hydroxyl group, or a nitro group. And the alkyl group may be a straight chain or branched chain alkyl group. For example, the alkenyl group having 2 to 10 carbon atoms may be an unsubstituted alkenyl group such as a vinyl group, a propenyl group, or a heptenyl group, or a substituted alkenyl group such as a halogen, an alkyl group, or a nitro group. For example, the alkynyl group having 2 to 10 carbon atoms may be an unsubstituted alkynyl group such as an ethynyl group, propynyl group or butynyl group, or an alkynyl group substituted with a halogen, an alkyl group, a nitro group or the like. The heteroaryl group having 6 to 40 carbon atoms may be a substituted or unsubstituted heteroaryl group such as a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a triazolyl group, a piperazinyl group, or a benzotriazolyl group, and the heteroaryl group may be a group bonded via a heteroatom or a group bonded via a carbon atom constituting a heteroaryl ring. For example, the aryl group having 6 to 40 carbon atoms may be an unsubstituted monocyclic aryl group such as a benzene ring, a substituted monocyclic aryl group such as a benzyl group, an ortho-substituted benzene ring, a meta-substituted benzene ring, a para-substituted benzene ring, or a homotrisubstituted benzene ring (wherein the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group, or the like), a condensed unsubstituted aryl group such as anthracene or phenanthrene, a condensed substituted aryl group such as substituted anthracene or phenanthrene, or a biphenyl groupOr a substituted or unsubstituted non-fused aryl group such as a benzophenone group. For example, the alkoxy group having 1 to 20 or 1 to 10 carbon atoms may be an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, or an isopropoxy group, or a substituted alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, which is substituted with a substituent such as a halogen group, a cyano group, a hydroxyl group, or a nitro group. For example, the C1-20 alkyl-substituted amino group may be CH3NH2-、(CH3)2NH-、C2H5NH2-、(C2H5)2NH-、C5H12NH2-、(C5H12)2NH-etc. CnH2n+ 1NH2-or (C)nH2n+1)2NH-an alkyl group having 1 to 20 carbon atoms, wherein n is an integer, or an amino group substituted with an alkyl group having 1 to 20 carbon atoms which is further substituted. For example, the aryl-substituted amine group having 6 to 20 carbon atoms may be a tertiary amine group in which two benzene rings are connected or a primary amine group in which one benzene ring is connected, and the benzene ring may be further substituted, and the benzene ring may be substituted with a non-condensed aryl group such as biphenyl or a condensed aryl group such as anthracene or phenanthrene. For example, the alkanoyl group having 2 to 20 carbon atoms may be acetyl, propionyl, hexanoyl, or the like. For example, the C6-C20 aryl-substituted acyl group may be an aryl-substituted acyl group such as an acetyl group substituted with a benzene ring or an acetyl group substituted with a benzene ring. The C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl and C5-C20 trialkylsilylkynyl may be selected from-Si (Me)3、(C2H5)3Si-、(C5H12)3Si-etc. (C)nH2n+1)3Silyl radicals of Si-, n being an integer, or-Si (Me)2C2H5、Me(C2H5)2Si-, etc.; or Me (C)2H3)2Si-etc. CnH2n+12(CnH2n-1)2Si-, etc., or Me2C2H3Si-etc. (C)nH2n+1)2(CnH2n-1) Si-, etc., or Me2C2HSi-et al (C)nH2n+1)2(CnH2n-3) Si-etc. or Me (C)2H)2Si-etc. CnH2n+1(CnH2n-3)2Si-, etc. n is an integer, and preferably n is 3 to 10, and the above alkyl group may be a further substituted alkyl group.
Further, R remains1-R6Independently selected from any one of hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2, 3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl, substituted or unsubstituted diarylamino and a group shown as R100 in the following structural formula,
in particular, when X1-X8When both are C, R remains1-R6Each independently selected from the group consisting of hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane, and substituted or unsubstituted cycloalkyl, and any one of the following R100 groups:
in addition, R remains1-R6May be the same group, may be completely different groups, may be partially the same group, and partially different groups, for example, the remainder R1-R5One is cyano, one is hydroxy or halogen atom, the last remaining R1-R6To getSubstituted or unsubstituted 9-carbazolyl is the remainder R1-R6All are different groups, although other groups, either the same group or some groups may be used. The embodiments of the present invention will not be described in detail.
Further, X' is any one selected from O, S, -NH-, C1-C20 substituted amine group, substituted or unsubstituted saturated alkyl group and substituted silane group; preferably, X' is selected from any one of O, S, -NH-, C1-C20 substituted amine groups, C1-C10 unsubstituted saturated alkyl groups, C3-C20 trialkylsilyl groups, C4-C20 trialkylsilylalkyl groups, C5-C20 trialkylsilylalkenyl groups and C5-C20 trialkylsilylkynyl groups; preferably, X' is selected from O, S, -NH-, - (Me)2and-Si (Me)3Any one of them.
Note that the substituted amine group may be CH3NH2-、(CH3)2NH-、C2H5NH2-、(C2H5)2NH-、C5H12NH2-、(C5H12)2NH-etc. CnH2n+1NH2-or (C)nH2n+1)2NH-alkyl substituted amino with 1-20 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-butyl group, or an alkyl group substituted with a substituent such as a halogen, a hydroxyl group, or a nitro group. And the alkyl group may be a straight chain or branched chain alkyl group. The C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl and C5-C20 trialkylsilylkynyl may be selected from-Si (Me)3、(C2H5)3Si-、(C5H12)3Si-etc. (C)nH2n+1)3Silyl radicals of Si-, n being an integer, or-Si (Me)2C2H5、Me(C2H5)2Si-, etc.; or Me (C)2H3)2Si-etc. CnH2n+12(CnH2n-1)2Si-, etc., or Me2C2H3Si-etc. (C)nH2n+1)2(CnH2n-1) Si-, etc., or Me2C2HSi-et al (C)nH2n+1)2(CnH2n-3) Si-etc. or Me (C)2H)2Si-etc. CnH2n+1(CnH2n-3)2Si-, etc. n is an integer, and preferably n is 3 to 10, and the above alkyl group may be a further substituted alkyl group.
The embodiment of the invention also provides a preparation method of the TADF material, which comprises the steps of selecting any one of the compounds and R1-R6To obtain the TADF material;
wherein Ra-Re are independently selected from the group consisting of1-R5And reacting to obtain the group of said TADF material. Specifically, the compound raw material is a substance in which at least 2 of Ra-Re in any compound shown in the general formula (A) are halogens, at least one of the Ra-Re is selected from any one of borate, pinacol borate and pinacol borate derivative groups, and the rest is H, and the halogens in the raw material and the borate, the pinacol borate and the pinacol borate derivative groups must exist so as to carry out subsequent reaction.
The method comprises the following steps: reacting the compound starting material with an R100-halogen such that the borate, the boronic acid pinacol ester and the boronic acid pinacol ester derivative group react with the halogen to form an intermediate 1 containing R100, and then reacting the intermediate 1 with a starting material containing the general formula (a) to form the TADF material. When intermediate 1 is formed, only the borate, boronic acid pinacol ester and boronic acid pinacol ester derivative groups react with the halogen to graft R100, while other groups in the starting material do not participate in the reaction. And when the intermediate 1 is reacted with the raw material containing the raw material of the general formula (a), only the halogen group of the intermediate 1 is reacted with the raw material containing the general formula (a), and then the general formula (a) is grafted to form the TADF material.
R100 corresponds to the remainder R1-R6That is to say that the starting R100-halogen may be a halogen containing residual R1-R6A radical source, and then reacting the halogen in the source with the borate, pinacol borate, and pinacol borate derivative radicals to form the remaining R1-R6Intermediate 1 of the group and then reaction of intermediate 1 with a feedstock comprising general formula (a) to form the TADF material.
For example, the present invention includes the following synthetic routes:
or the preparation method can be as follows: at least 3 of Ra-Re in any compound shown in a general formula (A) are halogens, the 3 halogens have different activities, R100-amino with higher activity in the compound raw materials reacts to form an intermediate 1 containing R100, and then the intermediate 1 reacts with the raw materials containing the general formula (a) to form the TADF material. Wherein, when the intermediate 1 is formed, the amido in the R100-amido reacts with the halogen with higher activity in the compound raw material, and the other halogen with lower activity does not react. Whereas when intermediate 1 is reacted with a starting material comprising a starting material of formula (a), only the remaining less reactive halogen groups of intermediate 1 are reacted with the starting material comprising formula (a) and subsequently grafted with formula (a) to form the TADF material.
For example, the present invention includes the following synthetic routes:
the embodiment of the invention provides a super-fluorescent material for preparing a light-emitting layer, wherein the light-emitting layer can be a single-color light-emitting layer emitting single colors such as red, green and blue. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
The super fluorescent material comprises the TADF material; further, it also includes a luminescent material. Preferably, it comprises 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material; more preferably, it comprises 20 to 40 parts by weight of the TADF material, 0.3 to 5 parts by weight of the luminescent material. The super-fluorescent material prepared by adopting the proportion can ensure that the formed luminescent material has good performance, so that the luminescent layer formed by the super-fluorescent material luminescent material has good performance.
More preferably, it further comprises a host material; and the triplet state energy level and the singlet state energy level of the host material are respectively higher than the triplet state energy level and the singlet state energy level of the TADF material, and the triplet state energy level and the singlet state energy level of the TADF material are respectively higher than the triplet state energy level and the singlet state energy level of the luminescent material. The main body material and the luminescent material with the specifications can be matched with the TADF material, so that the performance of the luminescent layer can be improved.
Specifically, the host Material may be selected from the host materials that can be used in combination with a fluorescent electroluminescent Material, a phosphorescent electroluminescent Material, a thermally activated delayed fluorescent luminescent Material, and the like in the prior art, and other host materials may also be selected, for example, the host materials described in advanced materials (advanced materials), 2017, 29, 1605444, Journal of Material Chemistry (Journal of Material Chemistry) C, 2016, 4, 11355-11381, Chemical Science (Chemical Science), 2016, 7, 3355-3363, Solid Films (Thin Solid Films), 2016, 619, 120-124, and the like may be used. In addition, since the TADF organic EL element requires high T1 energy in the host material of the light-emitting layer, the host material for the phosphorescent organic EL element described in chemical society reviews (Chemistry society reviews), 2011, 40, 2943-. Alternatively, the host material may be selected from at least one of the following compounds TDH 1-TDH 58:
or further, the host material is a compound having at least one structure selected from the group of partial structures (H-a) represented by the following formula, and at least one hydrogen atom in each structure in the group of partial structures (H-a) may be substituted by any one of the group of partial structures (H-a) or the group of partial structures (H-B), and at least one hydrogen in these structures may be substituted by deuterium, halogen, cyano, an alkyl group having a carbon number of 1 to 4 (e.g., methyl or tert-butyl), trimethylsilyl, or phenyl. The host material is preferably a compound having one to three structures selected from the group of partial structures (H-a) and one structure selected from the group of partial structures (H-B), and more preferably a compound having a carbazolyl group as the group of partial structures (H-a).
Further, the light emitting material may include, but is not limited to, one or a combination of the following FD1-FD 93.
the host material and the light-emitting material of the light-emitting layer described above are merely examples, and do not mean that only the above substances or combinations thereof can be used as the host material and the light-emitting material of the light-emitting layer in the embodiments of the present invention, and host materials and light-emitting materials of light-emitting layers that can satisfy the requirements in the prior art are also within the scope of the embodiments of the present invention.
Further, the TADF material provided by the embodiment of the present invention can also be used for producing a transfer layer, and therefore, the embodiment of the present invention also provides a transfer material for producing a transfer layer, which includes the above TADF material; the material also includes an electron transport material. Namely, the TADF material can be used for preparing an electron transport layer; it is also required that the lowest unoccupied rail of the electron transport material is lower than the lowest unoccupied rail of the TADF material; preferably, the difference between the lowest unoccupied orbital of the electron transport material and the lowest unoccupied orbital of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2 eV. The electron transport material and the TADF material can ensure that the electron transport material has good electron transport efficiency.
Specifically, the electron transport material can be selected from one or more of the following compositions shown as ET-1 to ET-57,
the electron transport materials described above are merely examples, and do not mean that only the above substances or combinations thereof can be used as the electron transport material according to the embodiments of the present invention, and electron transport materials satisfying the requirements in the prior art are also within the scope of the embodiments of the present invention.
Further, the transport layer provided by the embodiment of the present invention further includes a hole transport layer, and the transport material further includes a hole transport material; at this time, the TADF material may also be used in the preparation of the hole transport layer. The highest occupied orbit of the hole transport material is required to be higher than that of the TADF material, and preferably, the difference between the highest occupied orbit of the hole transport material and that of the TADF material is less than 0.5eV, preferably less than 0.3eV, and more preferably less than 0.2 eV. The performance of the hole transport material can be ensured by adopting the hole transport material.
Specifically, the hole transport material may be selected from, but not limited to, any one of phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives, or compounds represented by the following HT-1 to HT-34, or any combination thereof:
that is, the above TADF materials can be used for producing an electron transport layer and a hole transport layer, respectively.
Further, embodiments of the present invention also provide an electromechanical device, which includes at least one of the following layered structures:
(1) a light-emitting layer formed of the light-emitting material for producing a light-emitting layer described in the foregoing embodiment;
(2) a transfer layer formed of the transfer material for preparing a transfer layer according to the foregoing embodiment.
The organic electroluminescent device may be an Organic Light Emitting Diode (OLED), a light emitting electrochemical cell, an OLED sensor, in particular an organic light emitting diode, an organic solar cell, an organic transistor, an organic field effect transistor, an organic laser and a down conversion element.
The embodiments of the present invention are described by taking OLED as an example:
the organic electroluminescent device further comprises a cathode and an anode, i.e. a first electrode and a second electrode, wherein a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
Further, the first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
At least one layer of the layered structure described in the above (1) to (3) is provided between the cathode and the anode. And the layered structure is formed on the electrode by vacuum thermal evaporation, spin coating, printing, and the like.
Further, the organic electroluminescent device further includes a hole transport region, the hole transport region is located between the anode and the light emitting layer, and the hole transport region may be a Hole Transport Layer (HTL) having a single-layer structure, and the HTL may be an HTL provided by an embodiment of the present invention or may be formed of a hole transport material of the related art. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
Wherein the hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1-HI3 described below.
The light-emitting layer may be the light-emitting layer provided in the above embodiments of the present invention, or may be a light-emitting layer formed of a light-emitting material in the prior art. And in one OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
Further, the organic electroluminescent device further includes an electron transport region, an electron transport region between the light emitting layer and the cathode, the electron transport region may be an Electron Transport Layer (ETL) having a single-layer structure, and the electron transport region may also be a multi-layer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL). The electron transport layer may be the electron transport layer provided in the embodiments of the present invention, or may be an electron transport layer material formed of an electron transport material disclosed in the prior art.
An electron injection layer may also be included in the OLED device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li2O，Cs2CO3BaO, Na, Li and Ca.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a TADF material (with the number of TDS-007), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
under nitrogen, bromo-tert-butane (1.00 equiv.), 3, 5-difluoro-4-cyanophenylboronic acid (1.80 equiv.), and Pd2(dpa)3(0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100 ℃ for 16 h. The reaction mixture is then taken up in 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2 × 300mL), the organic phases are combined, the solvent is removed by rotary evaporation, filtered off with suction and washed with water to remove the salt, rinsed with ethanol, the filter cake is dried and column chromatographed (eluent: ethyl acetate: petroleum ether: 1:8) to give the intermediate as a solid, it being possible according to the invention to use the corresponding boronic esters instead of boronic acids.
Carbazole (2.40 equivalents) and the intermediate synthesized above (1.00 equivalent) were added to a two-necked round-bottomed flask equipped with a reflux condenser under nitrogen, cesium carbonate (4 equivalents) was added, and DMF (10 equivalents) was added to form a suspension, which was stirred at room temperature for 30 min. TDS-007(1.00 equivalent) was poured into the reaction solution all at once and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution and Na2SO4The solvent was removed and finally the crude product was purified by recrystallization from toluene or by 1:4 dichloromethane/petroleum ether and obtained as a solid. The actual mass spectrum measurement was 489.25.
Example 2
The embodiment of the invention provides a TADF material (with the number being TDS-022), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
bromoadamantane (1.00 equivalent), 3, 5-difluoro-4-cyanophenylboronic acid (1.80 equivalent), Pd under nitrogen2(dpa)3(0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100 ℃ for 16 h. The reaction mixture was then taken up in 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2X 300mL), the solvent was removed by rotary evaporation, filtered off with suction and washed with water
Salts, rinsing with ethanol, drying of the filter cake, column chromatography (eluent: ethyl acetate: petroleum ether 1:8) to give the intermediate as a solid, it being possible according to the invention to use the corresponding boronic esters instead of boronic acids.
Under the nitrogen condition, 3, 6-di-tert-butyl-9 h-pyrido [2,3-b ] is reacted]Indole (2.40 equivalents) and intermediate of the previous synthesis (1.00 equivalents) were added to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00mmol) was added, followed by DMF (100mL) to form a suspension, which was stirred at room temperature for 30 min. TDS-022(1.00 eq) was poured into the reaction mixture all at once and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution and Na2SO4The solvent was removed and finally the crude product was purified by recrystallization from toluene or by 1:4 dichloromethane/petroleum ether and the product was obtained as a solid with an actual mass spectrum measurement of 791.60.
Example 3
The embodiment of the invention provides a TADF material (with the number being TDS-040), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
diphenylamine (1.00 equivalent), 4-bromo-2, 6-difluorobenzonitrile (1.60 equivalent), tetrakistriphenylphosphine palladium (0.002 equivalent) and potassium carbonate (2 equivalent) are added into a three-necked flask which is replaced by nitrogen for three times, the three-necked flask is respectively added into a mixed solvent of toluene, ethanol and water (180 mL; 60 mL; 60mL), the temperature is increased to 110 ℃ for reflux reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, after the solid is separated out, the mixture is filtered, washed by water to remove the salt, rinsed by ethanol, a filter cake is dried, and column chromatography is carried out (eluent: ethyl acetate: petroleum ether: 1:8) to obtain a solid product.
Carbazole (2.40 equivalents) and the intermediate synthesized above (1.00 equivalent) were added to a two-necked round-bottomed flask equipped with a reflux condenser under nitrogen. Cesium carbonate (40.00mmol) was added, followed by DMF (100mL) to form a suspension, which was stirred at room temperature for 30 min. TDS-108(1.00 equivalent) was poured into the reaction solution all at once and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution, dried over Na2SO4, the solvent removed and finally the crude product obtained in solid form by recrystallization in toluene or by purification of 1:4 dichloromethane/petroleum ether. The actual mass spectrum measurement was 600.30.
Example 4
The embodiment of the invention provides a TADF material (with the number being TDS-108), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
under nitrogen, 3, 5-difluoro-4-cyanophenylboronic acid (1.00 eq), bromo-tert-butane (1.80 eq), Pd2(dpa)3(0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100 ℃ for 16 h. The reaction mixture is then taken up in 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2 × 300mL), the solvent is removed by rotary evaporation, the filtrate is filtered off and washed with water to remove the salt, rinsed with ethanol, the filter cake is dried and column chromatography (eluent: ethyl acetate: petroleum ether 1:8) gives the intermediate as a solid, it being possible according to the invention to use the corresponding boronic acid esters instead of boronic acids.
Under the nitrogen condition, the 12, 12-dimethyl-5, 12-dihydroindeno [1,2-c ] is reacted]Carbazole (2.40 equivalents) and the intermediate synthesized above (1.00 equivalent) were added to a two-necked round-bottomed flask equipped with a reflux condenser. Cesium carbonate (40.00mmol) was added, followed by DMF (100mL) to form a suspension, which was stirred at room temperature for 30 min. TDS-108(1.00 equivalent) was poured into the reaction solution all at once and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution and Na2SO4The solvent was removed and finally the crude product was purified by recrystallization from toluene or by 1:4 dichloromethane/petroleum ether and obtained as a solid. The actual mass measurement is: 721.38.
example 5
The embodiment of the invention provides a TADF material (with the serial number being TDS-117), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
deuterated carbazole (2.40 equivalents) was added under nitrogen to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00mmol) was added, followed by DMF (100mL) to form a suspension, which was stirred at room temperature for 30 min. 3, 5-difluorobenzonitrile (1.00 eq) was poured into the reaction solution all at once and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution and Na2SO4The solvent was removed and finally the crude product was purified by recrystallization from toluene or by 1:4 dichloromethane/petroleum ether and obtained as a solid. The actual mass spectrum measurement was 449.31.
Example 6
The embodiment of the invention provides a TADF material (with the serial number being TDS-123), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis route:
the specific process is as follows:
3, 6-dimethoxy-9 h-carbazole (2.40 equivalents) was added under nitrogen to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00mmol) was added, followed by DMF (100mL) to form a suspension, which was stirred at room temperature for 30 min. 2, 4-dibromothiophene-3-carbonitrile (1.00 equivalent) was poured into the reaction solution all at once, and stirred at 155 ℃ for 12 hours. Washed twice with saturated sodium chloride solution and Na2SO4The solvent was removed and finally the crude product was purified by recrystallization from toluene or by 1:4 dichloromethane/petroleum ether and obtained as a solid. The actual mass spectrum measurement was 559.20.
Other embodiments of TADF Material
The compound shown in the following structural formula is prepared according to the preparation method and is characterized by mass spectrum, and the results are shown in the following table:
verification example
In order to verify that the TADF material provided by the embodiment of the present invention can be used in an organic electroluminescent device (OLED), the present verification example provides a process for preparing an OLED:
transparent glass with ITO on the surface was used as a substrate, and then ultrasonically cleaned with deionized water, acetone, and ethanol for 15 minutes, respectively, and then treated in a plasma cleaner for 2 minutes.
Placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 4 × 10-5Pa, the deposition rate of the organic layer and the aluminum layer is 0.1-0.2 nm/s, the deposition rate of the LiF layer is 0.01nm/s, and the method comprises the following specific steps: under vacuum degree of 2X 10-4Under the conditions, the HT-8 described above on the anode layer film is vacuum evaporated to be used as a hole injection layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating the HI-3 on the hole injection layer as the hole injection layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 5 nm;
vacuum evaporation is carried out on the HT-32 as the hole transport layer of the device on the hole injection layer, the evaporation rate is 0.1nm/s, and the total film thickness is 45 nm;
vacuum evaporation is carried out on the hole transport layer, the HT-14 described in the previous paragraph is used as the hole transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness is 10 nm;
the light-emitting layer of the device is vacuum evaporated on the hole transport layer, the light-emitting layer comprises a main material, a TADF material and a light-emitting material, the main material is adjusted to be TDH-1-TDH-58 described in the above through a multi-source co-evaporation method, the evaporation rate is 0.1-0.2 nm/s, the TADF material TDS-001-TDS-133 provided by the embodiment of the invention is adjusted to be FD-1-FD-93 described in the above, the evaporation rate is 0.1nm/s, and the total thickness of the evaporated film is 25 nm;
vacuum evaporating an electron transport layer material ET-63 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 5 nm;
and (3) performing vacuum evaporation on the Electron Transport Layer (ETL) to form an ET-59+ Liq layer with the thickness of 25nm as the electron transport layer, wherein the weight ratio of the ET-59 to the LiQ layer is 1:1, and performing vacuum evaporation on the electron transport layer to form LiF with the thickness of 1nm and an Al layer with the thickness of 100nm as a cathode of the device.
Wherein the structural formulae of HT-8, HI-3, HT-32, HT-14, ET-63, ET-59, Liq and subsequently verified comparative compounds employed in comparative example 3 are as follows:
The specifically obtained verification examples of OLEDs are as follows:
verification example 1:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% TAS-007: 1% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 30% of the total mass, and the luminescent material FD-9 accounts for 1% of the total mass.
Verification example 2:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% TDS-007: 1% FD-72(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 provided in Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 30% of the total mass and the luminescent material FD-72 accounts for 1% of the total mass.
Verification example 3:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 29% TAS-007: 2% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 20% of the total mass, and the luminescent material FD-9 accounts for 2% of the total mass.
Verification example 4:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% TDS-022: 2% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-022 material provided in Synthesis example 2, wherein the luminescent material TDS-022 material accounts for 25% of the total mass, and the luminescent material FD-9 accounts for 2% of the total mass.
Verification example 5:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% TDS-108: 1% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-108 material provided in Synthesis example 4, wherein the luminescent material TDS-108 material accounts for 30% of the total mass, and the luminescent material FD-9 accounts for 1% of the total mass.
Verification example 6:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% TDS-117: 1% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-117 material provided in Synthesis example 5, wherein the luminescent material TDS-117 material accounts for 30% of the total mass, and the luminescent material FD-9 accounts for 1% of the total mass.
Verification example 7:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 28% TDS-117: 3% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TADF material provided in Synthesis example 5, wherein the luminescent material TDS-117 material accounts for 40% of the total mass, and the luminescent material FD-9 accounts for 3% of the total mass.
Verification example 8:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 28% TDS-123: 3% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TADF material provided in Synthesis example 6, wherein the luminescent material TDS-123 material accounts for 35% of the total mass, and the luminescent material FD-9 accounts for 5% of the total mass.
Verification example 9:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 28% TDS-007: 4% FD-72(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 provided by Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 30% of the total mass, and the luminescent material FD-72 accounts for 0.3% of the total mass.
Verification example 10 to verification example 23:
TDS-007 in the above-mentioned test example 1 was sequentially replaced with TDS-008, TDS-009, TDS-016, TDS-017, TDS-021TDS-024, TDS-040, TDS-118 and TDS-119 to obtain test examples 10 to 18.
Proof examples 19 and 20 were obtained by replacing TDS-007 in proof example 2 with TDS-008 and TDS-118 in this order. Verification of comparative example:
comparative examples were prepared with reference to the above-mentioned verification examples, which differ from the verification examples in that the TADF material was not used or directly used or the TADF material was used or the luminescent material or the transmitting material was used was different, specifically as follows:
verification comparative example 1:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 1% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), this comparative example being distinguished from example 1 by: the TADF material of example 1 was not added to the light-emitting layer.
Verification comparative example 2:
ITO (150nm)/HT-8(40nm)/HI-3(5nm)/HT-32(45nm)/HT-14(10nm)/TDH-14: 30% comparative compound 1% FD-9(25nm)/ET-63(5nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material comparative compound accounts for 30% of the total mass and the luminescent material FD-9 accounts for 1% of the total mass.
Verification comparative example 3:
ITO (150nm)/HI-3(5nm)/HT-14(10nm)/TDH-14: 30% TAS-001: 1% FD-9(25nm)/(ET-59+ LiQ) (25nm)/LiF (1nm)/Al (100nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 30% of the total mass, and the luminescent material FD-9 accounts for 1% of the total mass.
The following performance measurements were performed on the OLEDs prepared in the above-described verification examples and verification comparative examples:
the driving voltage and current efficiency of the OLED devices prepared in the verification examples 1 to 9 and the verification comparative examples 1 to 4 were measured at the same brightness using a digital source meter and a luminance meter. Specifically, the voltage is increased at a rate of 0.1V per second, and the voltage when the luminance of the OLED device reaches the required luminance, that is, the driving voltage, is measured, and the current density at that time is measured; the ratio of the brightness to the current density is the current efficiency;
OLED performance results
| Required brightness (cd/m2) | Operating voltage (V) | Current efficiency (cd/A) | External quantum efficiency (%) | |
| Verification example 1 | 1000 | 5.2 | 26.5 | 20.8 |
| Verification example 2 | 1000 | 4.4 | 27.1 | 22.6 |
| Verification example 3 | 1000 | 4.8 | 24.8 | 22.9 |
| Verification example 4 | 1000 | 4.9 | 26.1 | 23.2 |
| Verification example 5 | 1000 | 4.5 | 25.9 | 19.3 |
| Verification example 6 | 1000 | 5.1 | 25.6 | 20.9 |
| Verification example 7 | 1000 | 5.7 | 24.4 | 22.5 |
| Verification example 8 | 1000 | 5.6 | 24.2 | 22.6 |
| Verification example 9 | 1000 | 5.8 | 24.3 | 22.4 |
| Verification example 10 | 1000 | 4.5 | 26.7 | 23.1 |
| Verification example 11 | 1000 | 5.2 | 23.8 | 22.1 |
| Verification example 12 | 1000 | 5.1 | 24.7 | 21.9 |
| Verification example 13 | 1000 | 4.3 | 26.6 | 21.8 |
| Verification example 14 | 1000 | 5.0 | 25.9 | 22.1 |
| Verification example 15 | 1000 | 5.3 | 24.5 | 21.5 |
| Verification example 16 | 1000 | 4.6 | 26.3 | 19.9 |
| Verification example 17 | 1000 | 4.7 | 26.5 | 19.6 |
| Verification example 18 | 1000 | 4.2 | 26.4 | 21.7 |
| Verification example 19 | 1000 | 4.3 | 27.0 | 21.6 |
| Verification example 20 | 1000 | 4.4 | 26.2 | 22.6 |
| Verification of comparative example 1 | 1000 | 5.4 | 8.0 | 8.08 |
| Verification of comparative example 2 | 1000 | 4.6 | 10.0 | 11.3 |
| Verification of comparative example 3 | 1000 | 4.8 | 12.3 | 8.06 |
As can be seen from the above table, by comparing the verification examples 1 to 20 with the verification comparative examples 1 to 3, the synthesized compound of the present invention can effectively sensitize the dye and can realize effective energy transfer when being applied to a light emitting layer sensitizer in a device, thereby obtaining excellent device performance. The results show that the novel organic material provided by the invention is used for OLED devices, can effectively improve the current efficiency of the devices, and is an OLED material with good performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A TADF material, characterised in that it is a compound having any one of the following general formulae (1) or a tautomer thereof,
R1-R6at least one of them being a group of the formula (a), the remainder being R1-R6Each independently selected from any one of hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane and substituted or unsubstituted cycloalkyl;
and the general formula (a) satisfies at least one of the following conditions: (a) r25And R26Together form a single bond; (b) r27And R28Represent the atomic groups required to form together a substituted or unsubstituted benzene ring.
2. The TADF material according to claim 1, characterized in that when R is1-R6When one of them is a group of the formula (a), R1-R3Any one of them is a group represented by the general formula (a);
preferably, when R is1-R6When both are groups of the formula (a), R1And R3And is simultaneously a group of the formula (a), or R2And R4And is a group of the formula (a);
preferably, when R is1-R6When three of them are groups represented by the general formula (a), R1、R3And R4And is a group represented by the general formula (a).
3. The TADF material according to claim 1 or 2, characterized in that the group represented by the general formula (a) is any one of the following groups: substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2, 3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl or substituted or unsubstituted diarylamino;
preferably, the group of formula (a) is any one of the following groups of formula:
preferably, R32And R37Selected from the same substituent, R33And R36Selected from the same substituent, R34And R35Selected from the same substituent, R72And R79Selected from the same substituent, R73And R78Selected from the same substituent, R74And R77Are selected from the same substituent;
preferably, R31-R38、R41-R46、R51-R62And R71-R80Each independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane, and substituted or unsubstituted cycloalkyl;
preferably, R31-R38、R41-R46、R51-R62And R71-R80Each independently selected from any one of hydrogen, deuterated hydrogen, halogen, cyano, C1-C6 alkyl and C6-C10 aryl;
preferably, the group of formula (a) is any one of the following groups of formula:
preferably, any position of the benzene ring in the above formula can be replaced by N under the condition of satisfying the chemical bond relation;
more preferably, the group represented by the general formula (a) is any one of the following general formulae (1d) to (44 d):
preferably, the hydrogen in the benzene ring in any of the groups represented by the general formulae (1d) to (44d) is replaced by a deuterium atom;
preferably, R21-R28Each independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, C1-C6 alkyl and C6-C10 aryl;
preferably, any position of the benzene ring in the above formula may be replaced by N under the condition that the chemical bonding relation is satisfied.
4. The TADF material according to claim 1, characterized in that the residual R is1-R5Each independently selected from hydrogen, hydroxyl, halogen, cyano, nitro, C1-C20 substituted or unsubstituted saturated alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C6-C40 substituted or unsubstituted non-heteroaromatic group, C3-C40 substituted or unsubstituted heteroaromatic group, C1-C20 substituted or unsubstituted alkoxy, C1-C20 substituted or unsubstituted alkylthio, -any one of NH-, C1-C20 substituted amine, C2-C20 substituted or unsubstituted acyl, sulfonyl, C1-C10 alkyl substituted sulfonyl, amido, C1-C10 alkyl substituted amido, C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl, C5-C20 trialkylsilylkynyl, and C3-C20 substituted or unsubstituted cycloalkyl;
preferably, R remains1-R6Independently selected from hydrogen, hydroxyl, halogen, cyano, nitro, C1-C6 saturated alkyl, C3-C10 unsubstituted cycloalkyl, C6-C20 unsubstituted fused cycloalkyl, C6-C20 substituted non-fused and non-heteroaromatic group, C10-C40 substituted fused non-heteroaromatic group, C1-C10 alkyl substituted alkoxy, C1-C10 alkyl substituted alkylthio, -NH-, C1-C10 alkyl substituted amino, C6-C20 aromatic substituted amino, acyl, sulfonyl, C2-C10 alkyl acyl, C6-C20 aromatic substituted acyl, C1-C10 alkyl substituted sulfonyl, amido,Any one of C2-C8 alkyl substituted amido, C2-C8 alkyl substituted ester, C3-C15 trialkylsilyl, C4-C15 trialkylsilylalkyl, C5-C15 trialkylsilylalkenyl, C5-C15 trialkylsilylkynyl and C3-C15 substituted or unsubstituted cycloalkyl;
preferably, R remains1-R6Each independently selected from any one of hydrogen, cyano, carbazolyl, diarylamino, C3-C10 alkoxy, C1-C6 alkyl and C6-C10 aryl;
preferably, R remains1-R6Independently selected from any one of hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2, 3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl, substituted or unsubstituted diarylamino and a group shown in the following structural formula R100,
-Me -tBu
preferably, when X1-X8When both are C, R remains1-R6Each independently selected from the group consisting of hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane, and substituted or unsubstituted cycloalkyl, and any one of the following R100 groups:
-Me -tBu
preferably, X' is selected from any one of O, S, -NH-, C1-C20 substituted amine groups, substituted or unsubstituted saturated alkyl groups, and substituted silane groups;
preferably, X' is selected from any one of O, S, -NH-, C1-C20 substituted amine groups, C1-C10 unsubstituted saturated alkyl groups, C3-C20 trialkylsilyl groups, C4-C20 trialkylsilylalkyl groups, C5-C20 trialkylsilylalkenyl groups and C5-C20 trialkylsilylkynyl groups;
preferably, X' is selected from O, S, -NH-, - (Me)2and-Si (Me)3Any one of them.
5. A method of producing a TADF material according to any of claims 1-4, comprising: selecting any one of the compound raw materials shown in the following general formula (A) and R1-R6To obtain the TADF material;
wherein Ra-Re are independently selected from the group consisting of1-R6And reacting to obtain the group of said TADF material.
6. The method according to claim 5, wherein the compound starting material is a compound represented by the general formula (A) wherein at least 2 of Ra to Re are halogen, at least one selected from the group consisting of borate, pinacolato borate and pinacolato borate derivative, and the balance is H,
the method comprises the following steps: reacting the compound starting material with an R100-halogen such that the borate, the boronic acid pinacol ester and the boronic acid pinacol ester derivative group react with the halogen to form an intermediate 1 containing R100, and then reacting the intermediate 1 with a starting material containing the general formula (a) to form the TADF material.
7. A super luminescent material for producing a luminescent layer, characterized in that it comprises a TADF material according to any of claims 1 to 4;
preferably, it further comprises a luminescent material;
preferably, it comprises 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material;
more preferably, it comprises 20 to 40 parts by weight of the TADF material, 0.3 to 5 parts by weight of the luminescent material;
more preferably, it further comprises a host material;
more preferably, the triplet energy level and the singlet energy level of the host material are higher than the triplet energy level and the singlet energy level of the TADF material, respectively, and the triplet energy level and the singlet energy level of the TADF material are higher than the triplet energy level and the singlet energy level of the light-emitting material, respectively.
8. A transfer material for producing a transfer layer, characterized in that it comprises a TADF material according to any of claims 1-4;
preferably, the transport layer is an electron transport layer or a hole transport layer;
preferably, the transport material further comprises an electron transport material;
preferably, the lowest unoccupied rail of the electron transport material is lower than the lowest unoccupied rail of the TADF material;
preferably, the difference between the lowest unoccupied orbital of the electron transport material and the lowest unoccupied orbital of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2 eV.
9. The transport material of claim 8, wherein the transport material further comprises a hole transport material;
preferably, the highest occupied orbit of the hole transport material is higher than that of the TADF material,
preferably, the difference between the highest occupied orbital of the hole transport material and the highest occupied orbital of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2 eV.
10. An organic electroluminescent device, characterized in that it comprises at least one of the following layered structures:
(1) a light-emitting layer formed of the light-emitting material for producing a light-emitting layer according to claim 7;
(2) a transfer layer formed of the transfer material for producing a transfer layer according to claim 8;
preferably, the organic electroluminescent device is selected from organic light emitting diodes;
preferably, the organic electroluminescent device further comprises a cathode and an anode, and at least one layer of the layered structure of (1) or (2) above is disposed between the cathode and the anode.
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| CN115197184A (en) * | 2022-07-07 | 2022-10-18 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
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| CN104725298A (en) * | 2015-01-23 | 2015-06-24 | 南京工业大学 | Carbazole compounds, and synthesis and application thereof in OLEDs (Organic Light-Emitting diodes) |
| CN108264478A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | Carrier transmission material and carrier blocking layers and organic luminescent device |
| CN109705019A (en) * | 2019-01-29 | 2019-05-03 | 吉林大学 | Benzonitrile derivative and its preparing the application in electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725298A (en) * | 2015-01-23 | 2015-06-24 | 南京工业大学 | Carbazole compounds, and synthesis and application thereof in OLEDs (Organic Light-Emitting diodes) |
| CN108264478A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | Carrier transmission material and carrier blocking layers and organic luminescent device |
| CN109705019A (en) * | 2019-01-29 | 2019-05-03 | 吉林大学 | Benzonitrile derivative and its preparing the application in electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115197184A (en) * | 2022-07-07 | 2022-10-18 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
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