CN116715685A - Organic compound, application thereof and organic electroluminescent device comprising same - Google Patents
Organic compound, application thereof and organic electroluminescent device comprising same Download PDFInfo
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- CN116715685A CN116715685A CN202210183067.8A CN202210183067A CN116715685A CN 116715685 A CN116715685 A CN 116715685A CN 202210183067 A CN202210183067 A CN 202210183067A CN 116715685 A CN116715685 A CN 116715685A
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- substituted
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- heteroaryl
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 36
- -1 C1-C20 alkyl silicon Chemical class 0.000 claims description 100
- 239000010410 layer Substances 0.000 claims description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 59
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 125000001424 substituent group Chemical group 0.000 claims description 52
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 41
- 150000002431 hydrogen Chemical class 0.000 claims description 41
- 125000004104 aryloxy group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 229910052736 halogen Inorganic materials 0.000 claims description 30
- 150000002367 halogens Chemical class 0.000 claims description 30
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 29
- 125000001072 heteroaryl group Chemical group 0.000 claims description 28
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 26
- 125000001769 aryl amino group Chemical group 0.000 claims description 25
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 15
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 7
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 6
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000005669 field effect Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 2
- 150000001875 compounds Chemical group 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 238000003786 synthesis reaction Methods 0.000 description 26
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 150000004982 aromatic amines Chemical class 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- FDXXHPYFJDKWJS-UHFFFAOYSA-N 1-bromo-3-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC(Br)=C1 FDXXHPYFJDKWJS-UHFFFAOYSA-N 0.000 description 3
- 125000005264 aryl amine group Chemical group 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 2
- 229910052749 magnesium Inorganic materials 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
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- 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
- MOZHUOIQYVYEPN-UHFFFAOYSA-N 1-bromo-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Br)C=C1 MOZHUOIQYVYEPN-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006268 biphenyl-3-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C(*)=C([H])C([H])=C1[H] 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000006616 biphenylamine group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 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
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 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
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- 125000005592 polycycloalkyl group Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Materials Engineering (AREA)
Abstract
The invention relates to an organic compound and application thereof, and an organic electroluminescent device comprising the same, belonging to the technical field of organic luminescent materials. The organic compound has a structure represented by the following formula. The organic compound provided by the invention is beneficial to improving the efficiency and the service life of devices and is beneficial to adjusting the spectrum.
Description
Technical Field
The invention relates to an organic compound and application thereof, and an organic electroluminescent device comprising the same, belonging to the technical field of organic luminescent materials.
Background
With the continuous progress and development of social science, display technology becomes vital in people's life. Organic Light Emitting Diodes (OLEDs) are one of the currently mainstream display devices because of their advantages of flexibility, self-luminescence, high contrast, large size, low power consumption, etc.
The light-emitting mechanism of OLEDs is that electrons and holes recombine under electrical excitation to form excitons, which obey probability statistical distribution, with singlet excitons accounting for about 25% and triplet excitons accounting for about 75%. The first generation luminescence technology, which is collectively referred to as fluorescence technology, is luminescence using singlet excitons; the second generation luminescence technology is called phosphorescence technology, which utilizes triplet state excitons to emit light, and can theoretically achieve 100% internal quantum efficiency, but heavy metals required for constructing phosphorescent dyes are expensive and pollute the environment, so that the third generation thermal excitation delayed fluorescence technology constructed by using organic small molecules is commonly adopted at present, and when the energy level difference of single-triplet state is small, the triplet state excitons can cross to a singlet state between opposite systems, and then return to a ground state to emit light. Among them, red and green dyes, which are three primary colors, are the mainstream of the current commercial display devices because of their high electroluminescent efficiency and low power consumption. However, the chromaticity and lifetime of blue materials are not as good as the current commercial display requirements, and blue devices still use conventional fluorescent materials to achieve high color purity and long device lifetime.
Recently, a series of organic micromolecular materials DABCA-1 (adv. Mater.2016,28,2777-2781J. Mater.chem.C,2019,7, 3082-3089) based on boron-nitrogen resonance type thermal excitation delayed fluorescence are reported by the subject groups of Japanese Takuji Hatakeyama, junji Kido and the like, and boron atoms, nitrogen atoms and phenyl groups in the compounds form a rigid polycyclic aromatic resonance skeleton, so that the compound has higher fluorescence quantum yield. Compared with the traditional blue fluorescent dye, the compound has narrower emission spectrum band gap and higher color purity. However, the rigid planar structure also causes the energy level difference between the singlet state and the triplet state to be larger, the transition between the triplet state and the singlet state is slower, the exciton is compounded on the dye to cause serious efficiency roll-off, and the service life of the device is shorter. Furthermore, too planar a rigid structure often results in an adverse effect due to too high a doping concentration, which leads to a broadening of the emission spectrum and a red shift.
There is still a great room for improvement in the light emitting performance of the existing organic electroluminescent materials, and there is a need in the industry to develop new luminescent material systems to meet the commercial demands. Boron nitrogen resonance type materials have the advantages of high color purity and high luminous efficiency, and are attracting wide attention in the scientific research and industry. However, since the peripheral substituent has little influence on the energy level, that is, the light color of the material is difficult to regulate and control, the light color of the material is always limited to the sky blue region, and the further application of the material in the fields of high-resolution display, full-color display, white light illumination and the like is greatly limited.
As OLED products continue to enter the market, there is an increasing demand for the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, lifetime, cost, etc. The researchers of the present invention have discovered a smart molecular design through careful thought and continuous experimentation and are described in detail below. Surprisingly, the disclosed compounds are well suited for application in OLEDs and to enhance the performance of the device and to adjust its emission color to the deep blue range.
Disclosure of Invention
In order to solve the technical problems, the invention designs a boron-nitrogen structure-containing resonant fluorescent dye with a specific structure and capable of emitting deep blue light, and can effectively adjust the light color of a material to the deep blue light, and meanwhile, the efficiency and the service life of a device can be improved.
The invention provides a boron-nitrogen-containing organic compound, which has a structure shown in a general formula (1):
in the formula (1):
ring A, ring D, ring E, ring F each independently represent one of a substituted or unsubstituted C5-C60 aromatic ring, a substituted or unsubstituted C3-C60 heteroaromatic ring;
the substituents in ring A, ring D, ring E and ring F are each independently selected from at least one of halogen, unsubstituted or R ' substituted C1-C20 straight or branched alkyl, unsubstituted or R ' substituted C3-C20 cycloalkyl, unsubstituted or R ' substituted C1-C20 alkoxy, unsubstituted or R ' substituted C1-C20 alkylsilyl, unsubstituted or R ' substituted C1-C20 alkylamino, cyano, nitro, hydroxy, amino, unsubstituted or R ' substituted C6-C30 arylamino, unsubstituted or R ' substituted C3-C30 heteroarylamino, unsubstituted or R ' substituted C6-C30 aryloxy, unsubstituted or R ' substituted C3-C30 heteroaryloxy, unsubstituted or R ' substituted C6-C60 aryl and unsubstituted or R ' substituted C3-C60 heteroaryl;
The R' is selected from one or two of halogen, C1-C20 straight-chain or branched-chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxyl, C1-C20 alkyl silicon base, C1-C20 alkyl amino, C6-C30 aryl amino, C3-C30 heteroaryl amino, C6-C30 aryloxy, C3-C30 heteroaryl oxy, C6-C60 aryl and C3-C60 heteroaryl;
and the substituted substituents in the ring A, the ring D, the ring E and the ring F are not connected independently, or two adjacent substituent groups are connected through chemical bonds to form a ring;
L 1 、L 2 are respectively and independently a single bond, CR 1 R 2 、NR 3 S or O;
the R is 1 、R 2 、R 3 Each independently selected from one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C6-C60 aryl, and a substituted or unsubstituted C3-C60 heteroaryl;
n and m are 0 or 1, and n and m are not simultaneously 0, i.e. in formula (1), ring A and ring D are not linked to the benzene ring in the center of the formula or are each independently bound by L 1 、L 2 Respectively, and at least one of the ring A and the ring D is connected with the benzene ring in the center of the general formula.
Ra is a structure represented by formula (a);
in the formula (a), ar 1 And Ar is a group 2 Each independently represents one of a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group; and Ar is Ar 1 With Ar 2 Can be connected by chemical bonds;
R 1 、R 2 、R 3 、Ar 1 、Ar 2 the substituent groups of the substituent groups are independently selected from one or two of halogen, C1-C20 straight-chain or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxyl, C1-C20 alkyl silicon, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroaryl amino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl and C3-C60 heteroaryl.
Further, in the formula (1), the ring A, the ring D, the ring E and the ring F independently represent one of a substituted or unsubstituted C5-C60 aromatic ring and a substituted or unsubstituted C3-C60 heteroaromatic ring, and at least one of the ring A, the ring D, the ring E and the ring F has a structure represented by the formula (b 1) or the formula (b 2):
in the formula (b 1), c represents a shared chemical bond position where the formula (b 1) is linked to the formula (1); in formula (b 2), represents a radical attachment site;
Z 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ and Z 11 Are independently selected from CR 11 Or N, the R 11 Independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 heteroarylamino, and substituted or unsubstituted C6-C30 aryloxy One of a group, a substituted or unsubstituted C3 to C30 heteroaryloxy group, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted C3 to C60 heteroaryl group, or adjacent substituents may be linked to form one or more rings;
R 11 wherein the substituents are each independently selected from one or a combination of two of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxy, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl;
preferably, the Z 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C6-C60 arylamino, C6-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be joined to form one or more rings;
still preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
most preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from hydrogen, C1-C20 straight or branched alkyl, C6-C60 arylOr adjacent substituents may be linked together to form one or more rings.
In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or may be substituted with a plurality of substituents, and when the number of substituents is plural, the substituents may be selected from different substituents, and the same meaning is given when the same expression mode is involved in the present invention, and the selection ranges of the substituents are not repeated as shown above.
In the present specification, the expression of Ca to Cb means that the group has a carbon number of a to b, and unless otherwise specified, the carbon number generally excludes the carbon number of a substituent.
In the present specification, the expression "ring structure" means that the linking site is located at any position on the ring structure that can be bonded.
In the present specification, "each independently" means that the subject has a plurality of subjects, and the subjects may be the same or different from each other.
In the present invention, unless otherwise specified, the expression of a chemical element generally includes the concept of its isotope, for example, the expression of "hydrogen (H)", and includes its isotope 1 H (protium or H), 2 The concept of H (deuterium or D); carbon (C) then comprises 12 C、 13 C, etc., and are not described in detail.
Heteroatoms in the present invention generally refer to atoms or groups of atoms selected from N, O, S, P, si and Se, preferably selected from N, O, S.
In the present specification, examples of halogen include: fluorine, chlorine, bromine, iodine, and the like.
In the present invention, unless otherwise specified, both aryl and heteroaryl include cases of single rings and condensed rings.
In the present invention, the substituted or unsubstituted C6-C60 aryl group includes monocyclic aryl groups and condensed ring aryl groups, preferably C6-C30 aryl groups, and more preferably C6-C20 aryl groups. By monocyclic aryl is meant that the molecule contains at least one phenyl group, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are linked by a single bond, such as, for example: phenyl group,Biphenyl, terphenyl, and the like. Specifically, the biphenyl group includes a 2-biphenyl group, a 3-biphenyl group, and a 4-biphenyl group; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl. Condensed ring aryl refers to a group in which at least two aromatic rings are contained in the molecule, and the aromatic rings are not independent of each other but share two adjacent carbon atoms condensed with each other. Exemplary are as follows: naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, And a radical, a tetracenyl radical, a derivative thereof, and the like. The naphthyl comprises 1-naphthyl or 2-naphthyl; the anthracenyl is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl and 9-tetracenyl. The derivative group of the fluorene is selected from 9, 9-dimethylfluorenyl, 9-diethyl fluorenyl, 9-dipropyl fluorenyl, 9-dibutyl fluorenyl 9, 9-dipentylfluorenyl, 9-dihexylfluorenyl, 9-diphenylfluorenyl, 9-dinaphthylfluorenyl, 9' -spirobifluorene, and benzofluorenyl.
The C3-C60 heteroaryl groups mentioned in the present invention include monocyclic heteroaryl groups and condensed ring heteroaryl groups, preferably C3-C30 heteroaryl groups, further preferably C4-C20 heteroaryl groups, and still further preferably C5-C12 heteroaryl groups. Monocyclic heteroaryl means that the molecule contains at least one heteroaryl group, and when the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and are linked by a single bond, and examples of the monocyclic heteroaryl group include: furyl, thienyl, pyrrolyl, pyridyl, and the like. Condensed ring heteroaryl means a group in which at least one aromatic heterocyclic ring and one aromatic ring (aromatic heterocyclic ring or aromatic ring) are contained in a molecule and two adjacent atoms are fused together without being independent of each other. Examples of fused ring heteroaryl groups include: benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, acridinyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, dibenzocarbazolyl, indolocarbazolyl, and the like.
Specific examples of the arylene group in the present invention include divalent groups obtained by removing one hydrogen atom in the above examples of the aryl group. The number of carbons of the arylene group includes, but is not limited to, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, and the like. Specific examples of the heteroarylene group in the present invention include a divalent group obtained by removing one hydrogen atom in the above-mentioned heteroaryl group.
Examples of the aryloxy group in the present invention include monovalent groups composed of the above aryl group, heteroaryl group and oxygen.
In the present invention, an arylamino group represents a group formed by substituting hydrogen on an amino group with one or two aryl groups, wherein the attachment site of the arylamino group may be attached to an aryl group in the arylamino group or may be attached to N in the arylamino group, and exemplary carbon numbers and specific groups of the aryl group in the arylamino group are the same as those described above.
Examples of the C6-C30 arylamino group mentioned in the present invention include: phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrylamino, biphenylamino, and the like.
Examples of the C3-C30 heteroarylamino group mentioned in the present invention include: pyridylamino, pyrimidinylamino, dibenzofuranylamino and the like.
The chain alkyl group mentioned in the present invention includes a straight chain alkyl group and a branched chain alkyl group unless otherwise specified. Specifically, the substituted or unsubstituted C1-C30 chain alkyl group is preferably a substituted or unsubstituted C1-C16 chain alkyl group, more preferably a substituted or unsubstituted C1-C10 chain alkyl group. Examples of the substituted or unsubstituted C1-C10 chain alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl and the like.
In the present invention, the cycloalkyl group includes a monocycloalkyl group and a multicycloalkyl group; wherein, monocycloalkyl refers to an alkyl group having a single cyclic structure; polycycloalkyl refers to a structure in which two or more cycloalkyl groups are formed by sharing one or more ring carbon atoms; examples of the C3-C20 cycloalkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like.
In the present specification, examples of the C1-C10 alkoxy group which is preferably substituted or unsubstituted C1-C20 alkoxy group, and which is preferably substituted or unsubstituted C1-C10 alkoxy group, may be given as follows: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like are preferred, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy are more preferred.
In the present specification, as the substituted or unsubstituted C1-C20 silyl group, as the substituted or unsubstituted C1-C10 silyl group, a silyl group substituted with a group exemplified in the above-mentioned C1-C10 alkyl group may be exemplified, and specific examples thereof include: and methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, and the like.
It should be noted that the possible actions of the individual groups/features are described separately in the present application for convenience of explanation, but this does not mean that the groups/features are acting in isolation. In fact, the reason for obtaining good properties is essentially an optimal combination of the whole molecule, as a result of the synergy between the individual groups, rather than the effect of a single group.
Still further, the compound of the present application has a structure represented by the following formula (1-1) or (1-2):
in the formulae (1-1) and (1-2), ring A, ring D, ring E, ring F, L 1 、L 2 、Ar 1 、Ar 2 Is the same as that in formula (1).
Preferably, in the formulas (1-1) and (1-2), at least one of the rings E and F has a structure represented by the formula (b 1); still more preferably, at least one of the rings a and D has a structure represented by the formula (b 1) or (b 2).
Further, the compound of the present invention has a structure represented by the following formula (1-3) or (1-4):
in the formulae (1-3) and (1-4), the rings A, D, L 1 、L 2 、Ar 1 And Ar is a group 2 Is the same as that in formula (1);
Z 1 、Z 2 、Z 3 、Z 4 、Z 1 ’、Z 2 ’、Z 3 ’、Z 4 ' each independently selected from CR 12 Or N, the R 12 Independently selected from one of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
R 12 wherein the substituents are each independently selected from halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxy, C1-C20 alkylsilylOne or two of C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroaryl amino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl and C3-C60 heteroaryl.
Preferably, in the formulae (1-3) and (1-4), the Ar 1 With Ar 2 Are connected through chemical bonds;
and/or, preferably, in the formulas (1-3) and (1-4), at least one of the ring A and the ring D has a structure represented by the formula (b 1) or the formula (b 2);
further preferably, in the formulae (1-3) and (1-4), the ring A and the ring D each independently represent a structure represented by the formula (b 1) or the formula (b 2).
In the above general formula of the compound of the invention, ar is 1 And Ar is a group 2 Each independently is one of a substituted or unsubstituted C6-C60 aryl, a substituted or unsubstituted C3-C60 heteroaryl, and Ar 1 With Ar 2 Can be connected by chemical bonds;
preferably, the Ar 1 And Ar is a group 2 Each independently has a structure represented by formula (c), and Ar 1 With Ar 2 Can be connected by chemical bond:
in formula (c), represents a group attachment position;
Z 5 、Z 6 、Z 7 、Z 8 、Z 9 each independently is CR 13 Or N;
R 13 each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy Substituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents can be joined to form one or more rings;
R 13 wherein each of the substituted substituents is independently selected from one or a combination of two of halogen, C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxy, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl;
preferably, Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The method comprises the steps of carrying out a first treatment on the surface of the The R is 13 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylsilyl, C1-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl, or adjacent substituents may be joined to form one or more rings.
Further, the compound of the present invention has a structure represented by any one of the following formulas (1-5), (1-6), (1-7) or (1-8):
In the formulae (1-5), (1-6), (1-7) and (1-8), Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 Or N; r is R 13 Each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, andone of substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
R 13 wherein each of the substituted substituents is independently selected from one or a combination of two of halogen, C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxy, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl; preferably, Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylsilyl, C1-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl, or adjacent substituents may be linked to form one or more rings;
the Z is 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C6-C60 arylamino, C6-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be joined to form one or more rings;
preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
Most preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched chain alkyl, C6-C60 aryl, or adjacent substituents can be connected into one or more rings;
L 1 、L 2 is the same as that in formula (1).
Preferably, it has a structure as shown in the formula (1-7) or (1-8); most preferably, it has a structure as shown in the formula (1-8). Carbazole arylamine contrast: ra is preferably carbazole structure, is superior to carbazole and has stronger structural rigidity than arylamine, and can inhibit vibration and rotation of molecules, thereby reducing non-radiative transition rate of molecules and being beneficial to improving luminous efficiency.
Further preferably, in the above formulae (1-5), (1-6), (1-7) and (1-8): the Z is 1 、Z 2 、Z 3 、Z 4 、Z 1 ’、Z 2 ’、Z 3 ’、Z 4 ' each independently selected from CR 12 The R is 12 Independently selected from one of hydrogen, substituted or unsubstituted C1-C20 linear or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl;
more preferably, and Z 1 、Z 2 、Z 3 、Z 4 In (a): one is CR 12 R in (a) 12 Not hydrogen, while the other three are CR 12 R in (a) 12 Are all hydrogen, and Z 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: one is CR 12 R in (a) 12 Not hydrogen, while the other three are CR 12 R in (a) 12 Are all hydrogen; more preferably, and Z 1 、Z 2 、Z 3 、Z 4 In (a): one is CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen, and Z 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: one is CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen;
and/or, further preferably, Z 7 、Z 7 Each independently is CR 13 The method comprises the steps of carrying out a first treatment on the surface of the The R is 13 Each independently selected from one of hydrogen, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; more preferably, said R 13 Each independently selected from hydrogen, methyl, ethyl, isopropyl, t-butyl, isobutyl, and tert-pentyl;
and/or, further preferably, Z 5’ And Z is 5 Identical or different, Z 6’ And Z is 6 Identical or different, Z 7’ And Z is 7 Identical or different, Z 8’ And Z is 8 Identical or different, Z 9’ And Z is 9 Identical or different, Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ And Z is 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from one of hydrogen, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; more preferably, said R 13 Each independently selected from hydrogen. Because the HOMO and LUMO of the material are mainly distributed on the B-N parent nucleus structure and hardly distributed on carbazole and arylamine groups, further substitution on carbazole and arylamine can not further protect the molecular parent nucleus, and meanwhile, for the substituent group on carbazole, the C-C bond connected with carbazole can be weaker than the C-H bond Breakage is likely to occur during device operation, so that unsubstituted carbazole and aromatic amines are more advantageous over device lifetime.
Further preferably, Z 1 、Z 2 、Z 3 、Z 4 In (a): z is Z 2 Is CR (CR) 12 ，R 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen; and Z is 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: z is Z 2 ' CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen;
and/or, Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ And Z is 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from hydrogen;
and/or, the Z 1 、Z 2 、Z 3 、Z 4 In (a): z is Z 2 Is CR (CR) 11 ，R 11 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 11 R in (a) 11 Are all hydrogen; and Z is 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 In (a): z is Z 2’ Is CR (CR) 11 R in (a) 11 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 11 R in (a) 11 Are all hydrogen.
Still further preferably, the organic compound of the present invention has a structure represented by the formula (1-6) or (1-8); more preferably, it has a structure as shown in the formula (1-8).
In the above general formula of the compounds of the invention, L 1 、L 2 Are respectively and independently a single bond, CR 1 R 2 、NR 3 S or O, said R 1 、R 2 、R 3 Independently selected from one of methyl and phenyl Seed;
preferably, the L 1 、L 2 Each independently is a single bond, S or O;
more preferably, the L 1 、L 2 Representing a single bond.
Further, the organic compounds of the present invention may preferably be represented by the following specific structural compounds M1 to M122, which are merely representative and do not limit the scope of the present invention:
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the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification and is very suitable for industrial application.
As another aspect of the present invention, there is also provided the use of a compound as described above in an organic electroluminescent device. In particular, the compound of the present invention has excellent light-emitting properties, can give triplet excitons to achieve high light-emitting efficiency, and is suitable for use as a light-emitting dye based on its excellent carrier transport efficiency.
Of course, since the compound of the present invention can also be used as a sensitizer to realize a good light-emitting layer together with a host material and a dye. Devices for which applications include, but are not limited to, organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet scanners or electronic papers, preferably organic electroluminescent devices.
The invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and at least one or more luminescent functional layers interposed between the first electrode and the second electrode, wherein the luminescent functional layers contain at least one compound according to the invention.
The structure of the organic electroluminescent device is consistent with that of the existing device, for example, the organic electroluminescent device comprises an anode layer, a plurality of luminous functional layers and a cathode layer; the plurality of light-emitting functional layers include at least a light-emitting layer, wherein the light-emitting layer contains the above-described organic compound of the present invention.
The specific reasons for the excellent properties of the compounds of the present invention as luminescent dyes and/or sensitizer materials in the light-emitting layer of an organic electroluminescent device are not clear, and presumably the following reasons:
the invention uses a structure taking boron atoms and nitrogen atoms as a framework and uses L 1 And L 2 The benzene ring around the N atom is bonded with the central benzene ring, so that the molecular rigidity is improved, and simultaneously, the blue shift of light color can be regulated by introducing an arylamine group at the para position of the B atom, thereby meeting the light color requirement of a deep blue light device, further narrowing the emission spectrum and improving the color purity; meanwhile, because the HOMO and LUMO orbits of the structure are mainly distributed on the parent nucleus where the B atom and the N atom are located and are not distributed on the carbazole group below, the large steric hindrance of the carbazole group provides a protection effect for the parent nucleus, the compound decomposition caused by exciton quenching is prevented, the stability of the compound is improved, and meanwhile, the molecule vibration is inhibited by linkage, so that the improvement of the luminous efficiency is realized.
The OLED device prepared by the compound has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturing enterprises on high-performance materials.
Detailed Description
The technical scheme of the invention is further more specifically described below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The compounds of the present invention may be obtained by known methods, for example, synthesized by known organic synthesis methods. Exemplary synthetic routes are given below, but may be obtained by other methods known to those skilled in the art.
Synthesis example 1
Synthesis of compound M6:
synthesis of intermediate M6-1:
raw material A (30 g,71.27 mmol), 3-tert-butylbromobenzene (33.41 g,156.79 mmol), bis (di-tert-butyl-4-dimethylaminophosphine) palladium chloride (0.5 g,0.71 mmol), sodium tert-butoxide (27.4 g,285.07 mmol) and toluene (500 ml) were charged into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 110℃for reaction for 5 hours.
Cooling the system to room temperature, spin-drying the solvent, performing silica gel sample column chromatography to obtain a white solid, and recrystallizing with toluene and ethanol to obtain intermediate M6-140.2g.
Synthesis of intermediate M6-2:
m6-1 (40 g,58.36 mmol), carbazole (10.73 g,64.20 mmol), cesium carbonate (38.03 g,116.73 mmol), and N, N-dimethylformamide (500 ml) were put into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 100℃to react for 8 hours.
The system was cooled to room temperature, water (500 ml) was added dropwise to the system to precipitate a solid, which was filtered, and the cake was recrystallized from toluene/ethanol to give intermediate M6-243.7g.
Synthesis of product M6:
intermediate M6-2 (30 g,28.42 mmol) was added to a 2000ml three-necked flask, tert-butylbenzene (600 ml) was added, and after stirring for 20 minutes, the reaction system was cooled to 0℃and then tert-butyllithium (45.04 mL,1.6M,72.07 mmol) was added, and stirring was continued for 30 minutes while maintaining the low temperature. Then gradually heating to 60 ℃ and continuously heating for 2h. The reaction system temperature was again lowered to 0℃and boron tribromide (10.42 ml,108.10 mmol) was added under nitrogen protection, followed by stirring for 10 minutes and then heating to 60℃for 30 minutes. Diisopropylethylamine (22.82 ml,144.13 mmol) was added thereto after the temperature of the system was lowered to 0℃again, and the reaction system was heated to 120℃to react for 12 hours.
After the reaction was cooled to room temperature, the organic phase was dried under reduced pressure. Column chromatography gives 9.5g crude product, toluene/ethanol recrystallization gives 7.7g, purity 99.56%. Mass spectrometry determines molecular ion mass: 805.91 (theory: 805.92).
Synthesis example 2
Synthesis of compound M59:
synthesis of intermediate M59-1:
raw material B (30 g,48.92 mmol), 3-tert-butylbromobenzene (12.22 g,53, 81 mmol), bis (di-tert-butyl-4-dimethylaminophosphine) palladium chloride (0.33 g,0.49 mmol), sodium tert-butoxide (9.40 g,97.84 mmol) and toluene (500 ml) were put into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 110℃for reaction for 5 hours.
Cooling the system to room temperature, spin-drying the solvent, performing silica gel sample column chromatography to obtain a white solid, and recrystallizing with toluene and ethanol to obtain intermediate M6-132.6g.
Synthesis of intermediate M59-2:
m59-1 (35 g,46.08 mmol), carbazole (8.48 g,50.69 mmol), cesium carbonate (30.03 g,92.17 mmol), and N, N-dimethylformamide (500 ml) were put into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 100℃to react for 8 hours.
The temperature of the system was lowered to room temperature, water (500 ml) was added dropwise to the system to precipitate a solid, which was filtered, and the cake was recrystallized from toluene/ethanol to give intermediate M59-239.57g.
Synthesis of product M59:
this reaction is identical to the synthesis of M6, except that sufficient M6-2 is replaced by M59-2. 6.6g of the final product was finally obtained with a purity of 99.74%. Mass spectrometry determines molecular ion mass: 879.53 (theory: 879.53).
Synthesis example 3
Synthesis of compound M72:
synthesis of intermediate M72-1:
raw material C (30 g,59.39 mmol), 3-tert-butylbromobenzene (27.85 g,130.66 mmol), bis (di-tert-butyl-4-dimethylaminophosphine) palladium chloride (0.4 g,0.59 mmol), sodium tert-butoxide (11.42 g,118.78 mmol) and toluene (500 ml) were put into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 110℃for reaction for 5 hours.
Cooling the system to room temperature, spin-drying the solvent, performing silica gel sample column chromatography to obtain a white solid, and recrystallizing with toluene and ethanol to obtain intermediate M72-141.8g.
Synthesis of intermediate M72-2:
m72-1 (40 g,58.36 mmol), carbazole (10.73 g,64.20 mmol), cesium carbonate (38.03 g,116.73 mmol), and N, N-dimethylformamide (500 ml) were put into a 1000ml three-necked flask, nitrogen was replaced 3 times, and the temperature was raised to 100℃to react for 8 hours.
The system was cooled to room temperature, water (500 ml) was added dropwise to the system to precipitate a solid, which was filtered, and the cake was recrystallized from toluene/ethanol to give intermediate M72-243.7g.
Synthesis of product M72:
this reaction is identical to the synthesis of M6, except that sufficient M6-2 is replaced with M72-2. 3.9g of the final product was finally obtained with a purity of 99.63%. Mass spectrometry determines molecular ion mass: 1001.68 (theory: 1001.68).
Synthesis example 4
Synthesis of Compound M121:
synthesis of intermediate M121-1:
raw material D (30 g,61.24 mmol), diphenylamine (11.40 g,67.37 mmol), bis (di-t-butyl-4-dimethylaminophosphine) palladium chloride (0.41 g,0.61 mmol), sodium t-butoxide (11.77 g,122.49 mmol) and toluene (500 ml) were put into a 1000ml three-necked flask, nitrogen was substituted for 3 times, and the temperature was raised to 110℃for reaction for 5 hours.
Cooling the system to room temperature, spin-drying the solvent, performing silica gel sample column chromatography to obtain a white solid, and recrystallizing with toluene and ethanol to obtain 121-150.3g of intermediate M.
Synthesis of intermediate M121-2:
m121-1 (40 g,69.19 mmol), 4-isopropyl bromobenzene (13.77 g,69.19 mmol), bis (di-t-butyl-4-dimethylaminophosphine) palladium chloride (0.46 g,0.61 mmol), sodium t-butoxide (11.77 g,122.49 mmol) and toluene (500 ml) were put into a 1000ml three-necked flask, purged with nitrogen 3 times, and heated to 100℃for 8 hours.
Cooling the system to room temperature, spin-drying the solvent, performing silica gel sample column chromatography to obtain a white solid, and recrystallizing with toluene and ethanol to obtain intermediate M121-234.7g.
Synthesis of product M121:
this reaction is identical to the synthesis of M6, except that sufficient M6-2 is replaced with M121-2. 4.2g of the final product was finally obtained with a purity of 99.58%. Mass spectrometry determines molecular ion mass: 696.34 (theory: 696.34).
Synthesis of comparative example 1
Synthesis of compound R1:
in the process of synthesizing the compound R1, the target product cannot be obtained according to the method, and the intermediate containing the trimethylsilyl group is decomposed, presumably because the trimethylsilyl group is unstable under an acidic condition, and boron tribromide is an acidic compound, so that the intermediate is decomposed.
Device embodiment
Description of the embodiments
The OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. A Thin Film Transistor (TFT) may be provided on a substrate for a display.
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 the anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), or the like, and any combination thereof may be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combinations thereof may be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compounds used as the organic material layer may be small organic molecules, large organic molecules and polymers, and combinations thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region may have 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 HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant-containing polymers such as polystyrene, 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 such as the compounds shown below HT-1 to HT-51; or any combination thereof.
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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 of the compounds HT-1 through HT-51 described above, or one or more of the compounds HI-1 through HI-3 described below; one or more compounds of HT-1 through HT-51 may also be used to dope one or more of HI-1 through HI-3 described below.
The luminescent layer comprises luminescent dyes (i.e. dopants) that can emit different wavelength spectra, and may also comprise Host materials (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The plurality of monochromatic light emitting layers with different colors can be arranged in a plane according to the pixel pattern, or can be stacked together 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 simultaneously emitting different colors such as red, green, and blue.
According to different technologies, the luminescent layer material can be made of different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescence luminescent material and the like. In an OLED device, a single light emitting technology may be used, or a combination of different light emitting technologies may be used. The different luminescent materials classified by the technology can emit light of the same color, and can also emit light of different colors.
In one aspect of the invention, the light-emitting layer employs fluorescence electroluminescence technology. The luminescent layer fluorescent host material thereof may be selected from, but is not limited to, one or more combinations of BFH-1 to BFH-17 listed below.
In one aspect of the invention, an Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may employ, but is not limited to, one or more compounds of HT-1 through HT-51 described above, or one or more compounds of PH-47 through PH-77 described below; mixtures of one or more compounds of HT-1 through HT-51 and one or more compounds of PH-47 through PH-77 may also be employed, but are not limited thereto.
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The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single layer structure including a single layer electron transport layer containing only one compound and a single layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, combinations of one or more of ET-1 through ET-73 listed below.
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In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may employ, but is not limited to, one or more of the compounds ET-1 to ET-73 described above, or one or more of the compounds PH-1 to PH-46; mixtures of one or more compounds of ET-1 to ET-73 with one or more compounds of PH-1 to PH-46 may also be employed, but are not limited to.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following.
LiQ,LiF,NaCl,CsF,Li 2 O,Cs 2 CO 3 ,BaO,Na,Li,Ca，Mg，Yb。
The invention adopts Gaussian03 to carry out quantum chemical calculation on the compounds, adopts a time-dependent density functional method to respectively carry out theoretical calculation on the compounds listed in table 1, and the calculation results are shown in table 1. The fluorescence emission wavelength of the material is related to the first singlet energy level, and the higher the energy level, the shorter the fluorescence emission wavelength of the material, and the more blue the luminescence.
Table 1:
| numbering of compounds | S1/eV | Luminescence peak/nm |
| M1 | 2.91 | 426 |
| M6 | 2.92 | 425 |
| M15 | 2.89 | 429 |
| M33 | 2.88 | 431 |
| M121 | 2.88 | 431 |
| M122 | 2.89 | 429 |
| R2 | 2.80 | 443 |
| R3 | 2.82 | 440 |
| R4 | 2.98 | 415 |
| R5 | 2.78 | 446 |
| R6 | 2.79 | 443 |
As can be seen from the calculation data, the compound of the present invention has higher S1 state energy level and more blue light color compared with R2, R3, R5 and R6, which may be due to red shift of light color caused by the position of O atom in R2; the reason why the compounds of the present invention emit light more blue than the compounds R3, R5 and R6 may be that the luminescence blue-shifts due to the electron-induced effect generated by the carbazole group para to the B atom. Furthermore, the comparative compound R4 has a blue shift of more than 10nm with respect to the light color of the compound of the present invention, which may not be suitable for the application of the blue OLED device, which may be due to the widening of the band gap of the compound caused by the substitution of the N atom by the O atom, and the blue shift of the emission color.
From the spatial distribution of the front-line orbitals of the compound, the HOMO and LUMO orbitals of the compound are mainly distributed on the B-N parent nucleus, and almost no distribution exists on the lower aromatic amine groups, so that the lower aromatic amine groups can play a role in protecting the B-N parent nucleus to a certain extent.
The above results prove that the compound of the present invention is a fluorescent guest material with good performance.
The preparation process of the organic electroluminescent device in this embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in commercial cleaners, rinsed in deionized water, and rinsed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding surface with low-energy cation beam;
placing the glass substrate with anode in vacuum chamber, vacuumizing to<1×10 -5 Pa, vacuum thermal evaporation is carried out on the anode layer film in sequence, wherein 10nm of HT-4:HI-3 (97/3,w/w) mixture is used as a hole injection layer, 60nm of compound HT-4 is used as a hole transport layer, and 5nm of compound HT-14 is used as an electron blocking layer;
a representative specific compound M1 of the invention is selected to be used as a luminescent dye in a luminescent layer, and a binary mixture of 20nm compounds BFH-4:M1 (100:3, w/w) is selected as the luminescent layer;
5nm ET-23 as hole blocking layer, 25nm compound ET-69:ET-57 (50/50, w/w) mixture as electron transport layer, 1nm LiF as electron injection layer, 150nm metallic aluminum as cathode. The total evaporation rate of all organic layers and LiF was controlled at 0.1 nm/sec, and the evaporation rate of the metal electrode was controlled at 1 nm/sec.
Device examples 2 to 20 were fabricated in the same manner as in device example 1, except that the dopant in the light-emitting layer, i.e., the light-emitting dye, was different, and a specific dopant material was selected from representative specific compounds M2 to M122 of the present invention, and the scheme is shown in table 1 below.
Device comparative examples 1 to 5 were produced in the same manner as in device example 1 except that the dopants in the light-emitting layer were replaced with the compounds R2, R3, R4, R5 and R6 in the prior art, respectively.
Method for testing a device (including apparatus and test conditions):
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement,
external quantum efficiency (EQE%) of the resulting device can be directly tested on PR 650;
the lifetime test of LT95 is as follows: measured at 40mA/cm using a luminance meter 2 The initial brightness value of the device under the current density is kept constant, the time for the brightness of the device to drop to 97% of the initial brightness is measured, the unit is hours, the service life of the device in comparative example 1 is set to be 1.0, and the service life performances of the rest materials are all the ratio of the service life.
The performance data of the organic electroluminescent devices prepared in the examples and comparative examples of the respective devices are shown in Table 2 below.
Table 2:
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the results in table 2 show that when the resonant fluorescent dye with the boron-nitrogen structure is used as a luminescent dye in an organic electroluminescent device, compared with the comparative compounds R2, R3, R5 and R6 in the prior art, the compound can effectively improve the external quantum efficiency of the device and simultaneously effectively prolong the service life of the device, which is probably caused by better plane rigidity and structural stability. The compounds of the invention also show higher efficiency and better stability than the comparative compound R4, probably due to the R4 light color being too bluish, the exciton energy being too high and being more easily quenched by the host.
In the compound, ra in the general structure preferably contains carbazole structure, and the carbazole group has stronger structural rigidity compared with an arylamine group, so that vibration and rotation of molecules can be inhibited, the non-radiative transition rate of the molecules is reduced, and the luminous efficiency is improved. On the other hand, analysis shows that since HOMO and LUMO of the compound are mainly distributed on the B-N parent nucleus structure and are hardly distributed on carbazole groups and aromatic amine groups, further substitution on carbazole and aromatic amine cannot play a role in further protecting the molecular parent nucleus, and meanwhile, as for substituents on carbazole, C-C bonds connected with carbazole can be easily broken in the working process of a device, so that unsubstituted carbazole and aromatic amine are more advantageous in the service life of the device.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (14)
1. The structure of the boron-nitrogen-containing organic compound is shown as a general formula (1):
in the formula (1):
ring A, ring D, ring E, ring F each independently represent one of a substituted or unsubstituted C5-C60 aromatic ring, a substituted or unsubstituted C3-C60 heteroaromatic ring;
the substituent groups in the ring A, the ring D, the ring E and the ring F are respectively and independently selected from one of halogen, unsubstituted or R ' substituted C1-C20 straight-chain or branched alkyl, unsubstituted or R ' substituted C3-C20 cycloalkyl, unsubstituted or R ' substituted C1-C20 alkoxy, unsubstituted or R ' substituted C1-C20 alkyl silicon base, unsubstituted or R ' substituted C1-C20 alkylamino, cyano, nitro, hydroxyl, amino, unsubstituted or R ' substituted C6-C30 arylamino, unsubstituted or R ' substituted C3-C30 heteroaryl amino, unsubstituted or R ' substituted C6-C30 aryloxy, unsubstituted or R ' substituted C3-C30 heteroaryl, unsubstituted or R ' substituted C6-C60 aryl and unsubstituted or R ' substituted C3-C60 heteroaryl;
R' is selected from one or two combinations of halogen, C1-C20 straight-chain or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxyl, C1-C20 alkyl silicon base, C1-C20 alkyl amino, C6-C30 aryl amino, C3-C30 heteroaryl amino, C6-C30 aryloxy, C3-C30 heteroaryl oxy, C6-C60 aryl and C3-C60 heteroaryl; and the substituted substituents in the ring A, the ring D, the ring E and the ring F are not connected independently, or two adjacent substituent groups are connected through chemical bonds to form a ring;
L 1 、L 2 are respectively and independently a single bond, CR 1 R 2 、NR 3 S or O;
the R is 1 、R 2 、R 3 Each independently selected from one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C6-C60 aryl, and a substituted or unsubstituted C3-C60 heteroaryl;
n and m are 0 or 1, and n and m are not both 0;
ra is a structure represented by formula (a);
in the formula (a), ar 1 And Ar is a group 2 Each independently represents one of a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group; and Ar is Ar 1 With Ar 2 Can be connected by chemical bonds;
R 1 、R 2 、R 3 、Ar 1 、Ar 2 wherein each of the substituted substituents is independently selected from the group consisting of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxy, and combinations thereof,One or two of C1-C20 alkyl silicon group, C1-C20 alkyl amino group, C6-C30 aryl amino group, C3-C30 heteroaryl amino group, C6-C30 aryloxy group, C3-C30 heteroaryl oxy group, C6-C60 aryl group and C3-C60 heteroaryl group.
2. The organic compound according to claim 1, wherein in the formula (1), ring a, ring D, ring E, ring F each independently represents one of a substituted or unsubstituted C5 to C60 aromatic ring, a substituted or unsubstituted C3 to C60 heteroaromatic ring, and at least one of ring a, ring D, ring E, ring F has a structure represented by the formula (b 1) or formula (b 2):
in the formula (b 1), c represents a shared chemical bond position where the formula (b 1) is linked to the formula (1);
in formula (b 2), represents a radical attachment site;
Z 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ and Z 11 Are independently selected from CR 11 Or N, the R 11 Independently selected from one of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
R 11 Wherein the substituents are each independently selected from halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxy, C1-C20 alkylsilyl, C1-C20 alkyl-silyl, and C1-COne or two of C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl and C3-C60 heteroaryl;
preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C6-C60 arylamino, C6-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be joined to form one or more rings;
still preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
Most preferably, the Z 1 、Z 2 、Z 3 、Z 4’ 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched chain alkyl, C6-C60 aryl, or adjacent substituents can be connected into one or more rings.
3. The organic compound according to claim 1 or 2, which has a structure represented by the following formula (1-1) or (1-2):
in the formulae (1-1) and (1-2), ring A, ring D, ring E, ring F, L 1 、L 2 、Ar 1 And Ar is a group 2 Is the same as that in formula (1).
4. The organic compound according to claim 3, wherein at least one of the ring E and the ring F has a structure represented by the formula (b 1);
preferably, at least one of the rings a and D has a structure represented by formula (b 1) or formula (b 2).
5. The organic compound according to claim 3, which has a structure represented by the following formula (1-3) or (1-4):
in the formulae (1-3) and (1-4), the rings A, D, L 1 、L 2 、Ar 1 And Ar is a group 2 Is the same as that in formula (1);
Z 1 、Z 2 、Z 3 、Z 4 、Z 1 ’、Z 2 ’、Z 3 ’、Z 4 ' each independently selected from CR 12 Or N, the R 12 Independently selected from one of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
R 12 Wherein the substituents of the substituents are each independently selected fromHalogen, C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, nitro, cyano, amino, hydroxy, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl;
preferably, in the formulae (1-3) and (1-4), the Ar 1 With Ar 2 Are connected through chemical bonds;
and/or, preferably, in the formulas (1-3) and (1-4), at least one of the ring A and the ring D has a structure represented by the formula (b 1) or the formula (b 2);
further preferably, in the formulae (1-3) and (1-4), the ring A and the ring D each independently represent a structure represented by the formula (b 1) or the formula (b 2);
further preferably, in the formulae (1-3) and (1-4), the ring A and the ring D each independently represent a substituted or unsubstituted C5 to C60 aromatic ring.
6. The organic compound according to any one of claims 1 to 5, wherein Ar 1 And Ar is a group 2 Each independently is one of a substituted or unsubstituted C6-C60 aryl, a substituted or unsubstituted C3-C60 heteroaryl, and Ar 1 With Ar 2 Can be connected by chemical bonds;
Preferably, the Ar 1 And Ar is a group 2 Each independently has a structure represented by formula (c), and Ar 1 With Ar 2 Can be connected by chemical bond:
in formula (c), represents a group attachment position;
Z 5 、Z 6 、Z 7 、Z 8 、Z 9 each independently is CR 13 Or N;
R 13 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straightA chain or branched alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkylsilyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C6 to C60 arylamino group, a substituted or unsubstituted C3 to C60 heteroarylamino group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C3 to C30 heteroaryloxy group, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted C3 to C60 heteroaryl group, or one or more rings may be attached between adjacent substituents;
R 13 wherein each of the substituted substituents is independently selected from one or a combination of two of halogen, C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxy, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl;
Preferably, Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The method comprises the steps of carrying out a first treatment on the surface of the The R is 13 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylsilyl, C1-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl, or adjacent substituents may be joined to form one or more rings.
7. The organic compound according to claim 1 or 2, which has a structure represented by any one of the following formulas (1-5), (1-6), (1-7) or (1-8):
in the formulae (1-5), (1-6), (1-7) and (1-8), Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 Or N; r is R 13 Each independently selected from one of hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
R 13 Wherein each of the substituted substituents is independently selected from one or a combination of two of halogen, C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C1-C20 alkylamino, cyano, nitro, hydroxy, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl; preferably, Z 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from one of hydrogen, halogen, cyano, amino, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylsilyl, C1-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl, or adjacent substituents may be linked to form one or more rings;
the Z is 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from hydrogen, halogen, cyano, amino, C1-one of C20 straight or branched alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylsilyl, C6-C60 arylamino, C6-C60 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
Preferably, the Z 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, or adjacent substituents may be linked to form one or more rings;
most preferably, the Z 1 、Z 2 、Z 3 、Z 4 、Z 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 Each independently is CR 11 The R is 11 Each independently selected from one of hydrogen, C1-C20 straight or branched chain alkyl, C6-C60 aryl, or adjacent substituents can be connected into one or more rings;
L 1 、L 2 is the same as that in formula (1).
8. The organic compound according to claim 7, wherein Z 1 、Z 2 、Z 3 、Z 4 、Z 1 ’、Z 2 ’、Z 3 ’、Z 4 ' each independently selected from CR 12 The R is 12 Independently selected from one of hydrogen, C1-C20 straight chain or branched alkyl, C3-C20 cycloalkyl, C6-C60 aryl and C3-C60 heteroaryl;
preferably, the Z 1 、Z 2 、Z 3 、Z 4 、Z 1 ’、Z 2 ’、Z 3 ’、Z 4 ' each independently selected from CR 12 The R is 12 Independently selected from hydrogen, C1-C20 straight or branched alkylOne of C6-C60 aryl;
still more preferably, Z 1 、Z 2 、Z 3 、Z 4 In (a): one is CR 12 R in (a) 12 Not hydrogen, while the other three are CR 12 R in (a) 12 Are all hydrogen, and Z 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: one is CR 12 R in (a) 12 Not hydrogen, while the other three are CR 12 R in (a) 12 Are all hydrogen;
more preferably, Z 1 、Z 2 、Z 3 、Z 4 In (a): one is CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen, and Z 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: one is CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen;
and/or, further preferably, Z 7 、Z 7 ' each independently is CR 13 The R is 13 Each independently selected from one of hydrogen, C1-C10 straight or branched alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; more preferably, said R 13 Each independently selected from hydrogen, methyl, ethyl, isopropyl, t-butyl, isobutyl, and tert-pentyl;
and/or, further preferably, Z 5’ And Z is 5 Identical or different, Z 6’ And Z is 6 Identical or different, Z 7’ And Z is 7 Identical or different, Z 8’ And Z is 8 Identical or different, Z 9’ And Z is 9 Identical or different, Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ And Z is 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from hydrogen, C1-C10 straight or branched alkyl, C3-C10 ringOne of alkyl, C6-C30 aryl and C3-C30 heteroaryl; more preferably, said R 13 Each independently selected from hydrogen.
9. The organic compound according to claim 7 or 8, wherein Z 1 、Z 2 、Z 3 、Z 4 In (a): z is Z 2 Is CR (CR) 12 ，R 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen; and Z is 1 ’、Z 2 ’、Z 3 ’、Z 4 In's: z is Z 2 ' CR 12 R in (a) 12 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 12 R in (a) 12 Are all hydrogen;
and/or, Z 5’ 、Z 6’ 、Z 7’ 、Z 8’ 、Z 9’ And Z is 5 、Z 6 、Z 7 、Z 8 、Z 9 Each independently is CR 13 The R is 13 Each independently selected from hydrogen;
and/or, the Z 1 、Z 2 、Z 3 、Z 4 In (a): z is Z 2 Is CR (CR) 11 ，R 11 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 11 R in (a) 11 Are all hydrogen; and Z is 1’ 、Z 2’ 、Z 3’ 、Z 4’ And Z 11 In (a): z is Z 2’ Is CR (CR) 11 R in (a) 11 Methyl, ethyl, isopropyl, tert-butyl, isobutyl, tert-pentyl, while the other three are CR 11 R in (a) 11 Are all hydrogen.
10. The organic compound according to any one of claims 7 to 9, having a structure represented by formula (1 to 7) or (1 to 8);
preferably, it has a structure as shown in the formula (1-8).
11. The organic compound according to any one of claims 1, 3, 5, 7, 8, 9 or 10, wherein L 1 、L 2 Are respectively and independently a single bond, CR 1 R 2 、NR 3 S or O, said R 1 、R 2 、R 3 Each independently selected from one of methyl and phenyl;
preferably, the L 1 、L 2 Each independently is a single bond, S or O;
more preferably, the L 1 、L 2 Representing a single bond.
12. The organic compound according to claim 1, having the structure shown below:
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13. use of an organic compound according to any one of claims 1 to 12 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet scanner or an electronic paper;
preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device, more preferably as a light-emitting dye in a light-emitting layer.
14. An organic electroluminescent device comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain the organic compound according to any one of claims 1 to 12;
preferably, the light-emitting functional layer comprises an electron blocking layer and at least one of a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, and the light-emitting layer contains the organic compound according to any one of claims 1 to 12.
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