CN108530376B - Organic small molecule material based on 2, 6-dimethyl-4-cyanophenyl receptor unit and preparation and application thereof - Google Patents
Organic small molecule material based on 2, 6-dimethyl-4-cyanophenyl receptor unit and preparation and application thereof Download PDFInfo
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- CN108530376B CN108530376B CN201810435543.4A CN201810435543A CN108530376B CN 108530376 B CN108530376 B CN 108530376B CN 201810435543 A CN201810435543 A CN 201810435543A CN 108530376 B CN108530376 B CN 108530376B
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- -1 2, 6-dimethyl-4-cyanophenyl Chemical group 0.000 title claims abstract description 22
- 150000003384 small molecules Chemical class 0.000 title claims description 22
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Substances N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims description 146
- 239000010410 layer Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 239000002346 layers by function Substances 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 3
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 230000021615 conjugation Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000000921 elemental analysis Methods 0.000 description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- 239000012265 solid product Substances 0.000 description 18
- 238000005273 aeration Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 13
- 239000003480 eluent Substances 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000013067 intermediate product Substances 0.000 description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- AVXHSMPHQGFXRG-UHFFFAOYSA-N 4-bromo-3,5-dimethylbenzonitrile Chemical compound CC1=CC(C#N)=CC(C)=C1Br AVXHSMPHQGFXRG-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 6
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000001296 phosphorescence spectrum Methods 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 3
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- KHHIALZHPCMMMT-UHFFFAOYSA-N 10-(4-bromophenyl)phenoxazine Chemical compound C1=CC(Br)=CC=C1N1C2=CC=CC=C2OC2=CC=CC=C21 KHHIALZHPCMMMT-UHFFFAOYSA-N 0.000 description 2
- LAVLDGSVWFEKJG-UHFFFAOYSA-N 10-phenylphenoxazine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2N1C1=CC=CC=C1 LAVLDGSVWFEKJG-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 2
- AHDSYMVAUJZCOP-UHFFFAOYSA-N 9-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AHDSYMVAUJZCOP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LKCZFDAUYIBXGP-UHFFFAOYSA-N C1=CC=C2C(=C1)OC1=C(N2)C=CC=C1B1OC(C(C)(C)O1)(C)C Chemical compound C1=CC=C2C(=C1)OC1=C(N2)C=CC=C1B1OC(C(C)(C)O1)(C)C LKCZFDAUYIBXGP-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- FFEXBWMGHWXGSI-UHFFFAOYSA-N 10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxazine Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)O2)C2=C1 FFEXBWMGHWXGSI-UHFFFAOYSA-N 0.000 description 1
- JGGSOWGJMBNDHS-UHFFFAOYSA-N 10-phenyl-5h-phenazine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2N1C1=CC=CC=C1 JGGSOWGJMBNDHS-UHFFFAOYSA-N 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- CVVXUZRZYUJFDS-UHFFFAOYSA-N 3,6-ditert-butyl-9-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole Chemical compound C12=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC=C2N1C(C=C1)=CC=C1B1OC(C)(C)C(C)(C)O1 CVVXUZRZYUJFDS-UHFFFAOYSA-N 0.000 description 1
- KUBSCXXKQGDPPD-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical group C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 1
- GDKWMINSMJKPRT-UHFFFAOYSA-N 3-n,3-n,6-n,6-n-tetraphenyl-9h-carbazole-3,6-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C3=CC(=CC=C3NC2=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 GDKWMINSMJKPRT-UHFFFAOYSA-N 0.000 description 1
- IVURTNNWJAPOML-UHFFFAOYSA-N 5,10-dihydrophenazine Chemical compound C1=CC=C2NC3=CC=CC=C3NC2=C1 IVURTNNWJAPOML-UHFFFAOYSA-N 0.000 description 1
- ADMPYRNBAYKWOL-UHFFFAOYSA-N 9-[3-carbazol-9-yl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 ADMPYRNBAYKWOL-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses an organic small molecular material based on a 2, 6-dimethyl-4-benzonitrile acceptor unit, and preparation and application thereof. The organic micromolecule material has a structural formula shown in a formula (I), wherein Ar represents a phenyl aromatic amine heterocycle or a phenyl aromatic amine donor unit. The material has a weaker intramolecular charge transfer state, so that fluorescence emission in a deep blue to ultraviolet range can be realized. Meanwhile, due to the very short effective conjugation length of the molecule, the material has a high triplet state energy level. In the application of the organic electroluminescent device, the bipolar donor-acceptor type photoelectric material can effectively solve the problem of unbalanced current carriers of the unipolar organic photoelectric material, thereby simplifying the structure of the device and improving the performance of the device.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic small molecular material based on a 2, 6-dimethyl-4-benzonitrile acceptor unit, and preparation and application thereof.
Background
The thermal activation delayed fluorescent material becomes an international research and development hotspot due to the comprehensive performance of the thermal activation delayed fluorescent material compared with the phosphorescent material containing heavy metal. The pure organic compound material has small single triplet splitting energy, and can effectively capture triplet excitons when being applied to a device, thereby realizing 100 percent of internal quantum efficiency of the organic electroluminescent device. In the key period of the organic light emitting diode industrialization explosion, the efficiency, the service life and the stability of the pure organic thermal activation delayed fluorescence light emitting device still need to be improved, and especially the service life parameters of the existing blue light devices still have a very large promotion space. In addition to a stable luminescent material, the stability of the host material is also an extremely critical factor in the stability of devices such as the toggle. In order to improve the efficiency and the service life of the organic photoelectric device, compared with a polymer material, the organic small molecule host material has the advantages of fewer preparation steps, stable structure and convenient purification, so that higher device efficiency and longer device service life can be obtained, and the organic small molecule host material is more likely to be commercially applied. The use of small molecules as functional materials and the fabrication of flexible devices has received great attention and great progress because of their incomparable advantages over inorganic materials.
So far, organic small molecule photoelectric functional materials based on 2, 6-dimethyl-4-benzonitrile acceptor unit and phenyl aromatic amine heterocycle or phenyl aromatic amine donor unit are rarely reported.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide an organic small molecular material based on a 2, 6-dimethyl-4-benzonitrile acceptor unit. The organic micromolecule material contains a 2, 6-dimethyl-4-benzonitrile acceptor unit and a phenyl aromatic amine heterocycle or a phenyl aromatic amine donor unit.
The invention also aims to provide a preparation method of the organic small molecule material based on the 2, 6-dimethyl-4-cyanophenyl acceptor unit.
The invention further aims to provide application of the organic small molecule material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit in organic photoelectric devices.
The purpose of the invention is realized by the following technical scheme:
an organic small molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit has a structural formula shown in a formula (I):
wherein Ar represents a phenyl aromatic amine heterocycle or a phenyl aromatic amine donor unit represented by (1) to (25):
the preparation method of the organic small molecule material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit comprises the following steps: the intermediate shown in the formula (II) is prepared by Suzuki or Buchwald-Hartwig coupling reaction,
the application of the organic small molecular material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit in the organic photoelectric device is provided.
Furthermore, the organic photoelectric device comprises a substrate, an anode layer, a plurality of organic functional layer units and a cathode layer which are sequentially formed on the substrate; the organic functional layer unit comprises a hole injection layer, a hole transport layer, one or more light emitting layers and an electron transport layer; the preparation material of the light-emitting layer comprises one or more than two of the organic small molecule materials based on the 2, 6-dimethyl-4-benzonitrile acceptor unit.
The principle of the invention is as follows: the invention designs an organic micromolecule photoelectric functional main body material based on a 2, 6-dimethyl-4-benzonitrile acceptor unit and a phenyl aromatic amine heterocycle or a phenyl aromatic amine donor unit, wherein a cyano unit of the organic micromolecule photoelectric functional main body material has excellent electron injection and transmission capability, and the phenyl aromatic amine heterocycle and the phenyl aromatic amine unit have excellent hole injection and transmission capability. In this molecular design: 1. due to the existence of the bridging benzene ring, the charge transfer state in the molecule is effectively weakened, so that the luminescence is positioned in an ultraviolet interval, and the material is suitable for being used as a main material of a blue light material; 2. due to the existence of the bridging benzene ring and the effectively prolonged donor-acceptor distance, the relaxation of the molecular excited state structure is effectively inhibited, the stable state of the molecules in the device driving process is favorably maintained, and the important effect on maintaining high carrier mobility and stabilizing the device driving is achieved; 3. the polyaromatic amine heterocyclic substituted and polyaromatic amine substituted phenyl donor effectively improves molecular weight and structural rigidity, thereby realizing high thermal stability of the material; 4. since the conjugation is effectively interrupted, but only two methyl groups are introduced, and the existence of almost vertical dihedral angles is avoided, the triplet state of the molecule is kept at a high level, and the reduced dihedral angles keep the material with good carrier transport characteristics. The structure of molecular rigidity, proper molecular weight and good thermal stability are beneficial to improving the efficiency and stability of the device. The organic micromolecule has a single structure, determined molecular weight and simple purification steps, and can be applied to organic photoelectric devices such as organic light emitting diodes.
The organic micromolecular material has the following advantages and beneficial effects:
(1) the organic micromolecule photoelectric functional material based on the 2, 6-dimethyl-4-benzonitrile receptor unit and the phenyl aromatic amine heterocycle or the phenyl aromatic amine donor unit has the advantages of single structure, definite molecular weight, convenience in purification and good reproducibility of multiple synthesis.
(2) The organic micromolecule photoelectric functional material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit and the phenyl aromatic amine heterocycle or the phenyl aromatic amine donor unit has lower sublimation temperature and higher decomposition temperature, and the film form is stable.
(3) The organic micromolecular photoelectric functional material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit and the phenyl aromatic amine heterocycle or the phenyl aromatic amine donor unit can effectively solve the problem of unbalanced current carriers of a unipolar material in an organic semiconductor device, and can simplify the structure and improve the performance of the device when an organic photoelectric device is prepared.
(4) The conjugation length of the material molecule can be effectively regulated and controlled by changing the chemical structure of connection, and the energy levels of the highest occupied orbit and the lowest unoccupied orbit are regulated to meet the requirements of the organic photoelectric device.
(5) The physical properties of the material can be further improved by changing the modification group on the aromatic structure, and the material can endow the device with more excellent performance when being applied to an organic semiconductor device.
Drawings
FIGS. 1 to 4 are graphs of the relationship between current density and voltage and luminance, graphs of the relationship between current efficiency and luminance and power efficiency, graphs of the relationship between external quantum efficiency and luminance, and electroluminescence spectra of the organic electroluminescent devices obtained in examples 26 to 28, respectively.
FIG. 5 is a graph showing fluorescence spectrum and phosphorescence spectrum of 2, 6-dimethyl-4-benzonitrile acceptor unit-based organic small molecule material of formula 18 used in examples 27 to 28 under pure film condition.
FIG. 6 is a graph showing a fluorescence spectrum and a phosphorescence spectrum under a toluene solution of a luminescent guest compound SPDMAc-TRZ used in examples 26 to 28.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based organic small molecule material having structural formula 1:
(1) synthesis of intermediate 1: under the atmosphere of nitrogen, in 250ml wide-mouth three183 mg of phenoxazine and 10 ml of bromobenzene were added to a round-bottomed reaction flask and dissolved in 70 ml of toluene solution. Subsequently, 5 g of potassium carbonate was added, and the mixture was stirred and aerated for 15 minutes. A solution of 44.6 mg of palladium acetate and 0.73 mg of tributylphosphine was then added, stirred for 30 minutes with aeration and subsequently heated to 110 ℃. The reaction was refluxed for 24 hours. After the reaction is stopped by cooling, the liquid in the reaction system is removed by rotary evaporation to obtain an intermediate product 10-phenyl-10H-phenoxazine. The molecular formula of the product is as follows: c18H13NO; molecular weight: 259.31, respectively; the elemental analysis results were: c, 83.37; h, 5.05; n, 5.40; and O, 6.17. The reaction formula is as follows:
(2) synthesis of intermediate 2: under nitrogen atmosphere, 220 mg of 10-phenyl-10H-phenoxazine was added to a 250ml three-necked round-bottomed reaction flask, followed by slowly adding 1.85 ml of liquid bromine dropwise and stirring for 5 hours. Then heated to 80 ℃ and refluxed for 2 hours. After the reaction was stopped by cooling, the acetic acid solvent was removed by rotary evaporation. The molecular formula of the product is as follows: c18H12BrNO; molecular weight: 338.20, respectively; the elemental analysis results were: c, 63.93; h, 3.58; br, 23.63; n, 4.14; o, 4.73; the reaction formula is as follows:
(3) synthesis of intermediate 3: under nitrogen atmosphere, 450 mg of pinacol diboron, 150 ml of dioxane and 300 mg of potassium acetate are sequentially added into a 250ml three-port round-bottom reaction bottle, the mixture is aerated and stirred for 30 minutes, and finally 100 mg of [1,1' -bis (diphenylphosphino) ferrocene is added]Palladium dichloride was introduced into the reactor for 30 minutes, heated to 85 ℃ and refluxed for 24 hours. And (4) after the reaction is stopped by cooling, removing the solvent of the reaction system by rotary evaporation. The molecular formula of the product is as follows: c24H24BNO3(ii) a Molecular weight: 385.27, respectively; elemental analysis results: c, 74.82; h, 6.28; b, 2.81; n, 3.64; o, 12.46. The reaction formula is as follows:
(4) and (3) final product: under nitrogen atmosphere, 420 mg of 4-bromo-3, 5-dimethylbenzonitrile and 10-phenyl-3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -10H-phenoxazine are added into a 250ml three-mouth round-bottom reaction bottle, then 120ml of toluene, 40ml of absolute ethanol and 40ml of 2mol/L aqueous solution of potassium carbonate are sequentially added, and the mixture is stirred and dissolved. After 15 minutes of aeration 50mg of tetrakis (triphenylphosphine) palladium (0) catalyst was added, and after 30 minutes of aeration, the reaction was heated to 85 ℃ and refluxed for 24 hours. And (4) after the reaction is stopped by cooling, removing the solvent of the reaction system by rotary evaporation. The reaction system was extracted with a dichloromethane solvent, and washed three times with deionized water, then three times with saturated brine, and dried over anhydrous magnesium sulfate for 1 hour. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane in a ratio of 3: 1. The product was finally obtained as a white solid in 69% yield. The molecular formula of the product is as follows: c27H20N2O; molecular weight: 388.16, respectively; the elemental analysis results were: c, 83.48; h, 5.19; n, 7.21; and O, 4.12. The reaction formula is as follows:
example 2
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecular material having structural formula 2:
compared with the example 1, the difference is that the phenoxazine is replaced by equivalent 9, 9-dimethyl-9, 10-dihydroacridine, and other raw materials and steps are the same as the example 1.
(1) Intermediate 1 has the formula: c21H19N; molecular weight: 285.39, respectively; elemental analysis results: c, 88.38; h, 6.71; and N, 4.91. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c21H18BrN; molecular weight: 364.29, respectively; elemental analysis results: c, 69.24; h, 4.98; br, 21.93; and N, 3.85. The reaction formula is as follows:
(3) intermediate 3 has the molecular formula: c27H30BNO2(ii) a Molecular weight: 411.35, respectively; elemental analysis results: c, 78.84; h, 7.35; b, 2.63; n, 3.41; and O, 7.78. The reaction formula is as follows:
(4) the final product was obtained in 71% yield as a white solid. The molecular formula of the product is as follows: c30H26N2(ii) a Molecular weight: 414.21, respectively; the elemental analysis results were: c, 86.92; h, 6.32; and N, 6.76. The reaction formula is as follows:
example 3
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 3:
the difference from example 1 is that phenoxazine was replaced with an equivalent amount of 10, 10-dimethyl-5, 10-dihydrodibenzo [ b, e ] [1,4] azaaniline and the other starting materials and procedures were the same as in example 1.
(1) Intermediate 1 has the formula: c20H19NSi, respectively; molecular weight: 301.46, respectively; elemental analysis results: c, 79.68; h, 6.35; n, 4.65; si, 9.32. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c20H18BrNSi; molecular weight: 380.36, respectively; elemental analysis results: c, 63.16; h, 4.77; br, 21.01; n, 3.68; si, 7.38. The reaction formula is as follows:
(3) intermediate 3 has the molecular formula: c26H30BNO2Si; molecular weight: 427.21, respectively; elemental analysis results: c, 73.06; h, 7.07; b, 2.53; n, 3.28; o, 7.49; si, 6.57. The reaction formula is as follows:
(4) the final yield of the solid product was 77%. The molecular formula of the product is as follows: c29H26N2Si; molecular weight: 430.19, respectively; the elemental analysis results were: c, 80.89; h, 6.09; n, 6.51; si, 6.52. The reaction formula is as follows:
example 4
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 4:
compared with the example 1, the difference is that the phenoxazine is replaced by 10H-phenothiazine with equivalent weight, and other raw materials and steps are the same as the example 1.
(1) Intermediate 1 has the formula: c18H13NS; molecular weight: 275.37, respectively; elemental analysis results: c, 78.51; h, 4.76; n, 5.09; and S, 11.64. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c18H12BrNS; molecular weight: 354.26, respectively; elemental analysis results: c, 61.03; h, 3.41; br, 22.55; n, 3.95; and S, 9.05. The reaction formula is as follows:
(3) intermediate 3 has the molecular formula: c24H24BNO2S; molecular weight: 401.33, respectively; elemental analysis results: c, 71.83; h, 6.03; b, 2.69; n, 3.49; o, 7.97; and S, 7.99. The reaction formula is as follows:
(4) the final product was obtained in 73% yield as a white solid. The molecular formula of the product is as follows: c27H20N2S; molecular weight: 404.13, respectively; the elemental analysis results were: c, 80.17; h, 4.98; n, 6.93; and S, 7.93. The reaction formula is as follows:
example 5
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 5:
the difference from example 1 is that the starting materials and procedure are the same as in example 1, except that the phenoxazine is replaced by an equivalent amount of 5, 10-dihydrophenazine and two equivalents of bromobenzene are added.
(1) Intermediate 1 has the formula: c24H18N2(ii) a Molecular weight: 334.42, respectively; the elemental analysis results were: c, 86.20; h, 5.43; and N, 8.38. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c24H17BrN2(ii) a Molecular weight: 413.32, respectively; elemental analysis results: c, 69.74; h, 4.15; br, 19.33; n, 6.78. The reaction formula is as follows:
(3) intermediate 3 has the molecular formula: c30H29BN2O2(ii) a Molecular weight: 460.38, respectively; elemental analysis results: c, 78.27; h, 6.35; b, 2.35; n, 6.08; o, 6.95. The reaction formula is as follows:
(4) the final yield of the solid product was 57%. The molecular formula of the product is as follows: c33H25N3(ii) a Molecular weight: 463.20, respectively; the elemental analysis results were: c, 85.50; h, 5.44; and N, 9.06. The reaction formula is as follows:
example 6
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecular material having structural formula 6:
(1) intermediate 1: under a nitrogen atmosphere, 183 mg of phenoxazine and 10 ml of p-dibromobenzene were added to a 250ml three-necked round-bottomed reaction flask and dissolved in 70 ml of a toluene solution. Subsequently, 5 g of potassium carbonate was added, and the mixture was stirred and aerated for 15 minutes. 44.6 mg of palladium acetate and 0.73 ml of tributylphosphine solution are subsequently added and stirred for 30 minutes under aeration. Then heated to 110 ℃ and refluxed for 24 hours. Removing the liquid in the reaction system by rotary evaporation to obtain an intermediate product, namely 10- (4-bromophenyl) -10H-phenoxazine. The molecular formula of the product is as follows: c18H12BrNO; molecular weight: 338.20, respectively; elemental analysis results: c, 63.93; h, 3.58; br, 23.63; n, 4.14; and O, 4.73. The reaction formula is as follows:
(2) intermediate 2: under nitrogen atmosphere, the 10- (4-bromophenyl) -10H-phenoxazine obtained in the previous step was added to a 250ml three-necked round-bottomed reaction flask, 15.6 g of pinacol diboron, 240 ml of dioxane, 24 g of potassium acetate were added, and the mixture was stirred under aeration for 30 minutes. Then 700 mg of [1,1' -bis (diphenylphosphino) ferrocene ] are added]Palladium dichloride was introduced into the reactor for 30 minutes, heated to 85 ℃ and refluxed for 24 hours. After the reaction is stopped by cooling, the solvent of the system is removed by rotary evaporation to obtain an intermediate product 10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -10H-phenoxazine, wherein the molecular formula of the product is C24H24BNO3(ii) a Molecular weight: 385.27, respectively; elemental analysis results: c, 74.82; h, 6.28; b, 2.81; n, 3.64; o, 12.46. The reaction formula is as follows:
(3) the final product: sequentially adding 10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -10H-phenoxazine obtained in the last step, 420 mg of 4-bromo-3, 5-dimethyl benzonitrile, 120ml of toluene, 40ml of absolute ethanol and 40ml of 2mol/L aqueous solution of potassium carbonate into a 250ml three-port round bottom reaction bottle under the atmosphere of nitrogen, stirring for dissolving, introducing gas for 15 min, adding 50mg of tetrakis (triphenylphosphine) palladium (0) catalyst, introducing gas for 30 min, heating to 85 ℃, refluxing for 24H, cooling to stop the reaction, removing the solvent of the reaction system by rotary evaporation, extracting the reaction system with dichloromethane solvent, washing with deionized water for three times, and washing with saturated saline water for three times, dried over anhydrous magnesium sulfate for 1 hour. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane in a ratio of 3: 1. The final yield of the solid product was 77%. The molecular formula of the product is as follows: c27H20N2O; molecular weight: 388.47, respectively; the elemental analysis results were: c, 83.48; h, 5.19; n, 7.21; and O, 4.12. The reaction formula is as follows:
example 7
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 7:
compared with example 6, the difference is that phenoxazine is replaced by equivalent 10H-phenothiazine, and other raw materials and steps are the same as example 6.
(1) Intermediate 1 has the formula: c18H12BrNS; molecular weight: 354.26, respectively; elemental analysis results: c, 61.03; h, 3.41; br, 22.55; n, 3.95; and S, 9.05. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c24H24BNO2S; molecular weight: 401.33, respectively; elemental analysis results: c, 71.83; h, 6.03; b, 2.69; n, 3.49; o, 7.97; and S, 7.99. The reaction formula is as follows:
(3) the final yield of the solid product was 73%. The molecular formula of the product is as follows: c27H20N2S; molecular weight: 404.13, respectively; the elemental analysis results were: c, 80.17; h, 4.98; n, 6.93; and S, 7.93. The reaction formula is as follows:
example 8
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecular material having structural formula 8:
the difference from example 6 is that 10H-phenoxazine was replaced with equivalent 9, 9-dimethyl-9, 10-dihydroacridine and the other starting materials and procedures were the same as in example 6.
(1) Intermediate 1 has the formula: c21H18BrN; molecular weight: 364.29, respectively; elemental analysis results: c, 69.24; h, 4.98; br, 21.93; and N, 3.85. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c27H30BNO2(ii) a Molecular weight: 411.35, respectively; elemental analysis results: c, 78.84; h, 7.35; b, 2.63; n, 3.41; and O, 7.78. The reaction formula is as follows:
(3) the final yield of the solid product was 69%. The molecular formula of the product is as follows: c30H26N2(ii) a Molecular weight: 414.21, respectively; the elemental analysis results were: c, 86.92; h, 6.32; and N, 6.76. The reaction formula is as follows:
example 9
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecular material having structural formula 9:
the difference from example 6 is that 10H-phenoxazine was replaced with an equivalent amount of 10, 10-dimethyl-5, 10-dihydrodibenzo [ b, e ] [1,4] azaaniline, and the other starting materials and procedures were the same as in example 6.
(1) Intermediate 1 has the formula: c20H18BrNSi; molecular weight: 380.36, respectively; elemental analysis results: c, 63.16; h, 4.77; br, 21.01; n, 3.68; si, 7.38. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c26H30BNO2Si; molecular weight: 427.43, respectively; elemental analysis results: c, 73.06; h, 7.07; b, 2.53; n, 3.28; o, 7.49; si, 6.57. The reaction formula is as follows:
(3) the final yield of the solid product was 72%. The molecular formula of the product is as follows: c29H26N2Si; molecular weight: 430.19, respectively; the elemental analysis results were: c, 80.89; h, 6.09; n, 6.51; si, 6.52. The reaction formula is as follows:
example 10
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based organic small molecule material having structural formula 10:
(1) the first step reaction was identical to that of example 5. Intermediate 1 has the formula: c18H14N2(ii) a Molecular weight: 258.32, respectively; elemental analysis results: c, 83.69; h, 5.46; n, 10.84. The reaction formula is as follows:
the remaining steps are compared with example 6, except that 10H-phenoxazine is replaced with an equivalent amount of 5-phenyl-5, 10-dihydrophenazine and the other starting materials and steps are the same as in example 6.
(2) Intermediate 2 has the molecular formula: c24H17BrN2(ii) a Molecular weight: 413.32, respectively; elemental analysis results: c, 69.74; h, 4.15; br, 19.33; n, 6.78. The reaction formula is as follows:
(3) intermediate 3 has the molecular formula: c30H29BN2O2(ii) a Molecular weight 460.38; elemental analysis results: c, 78.27; h, 6.35; b, 2.35; n, 6.08; o, 6.95. The reaction formula is as follows:
(4) the final yield of the solid product was 74%. The molecular formula of the product is as follows: c33H25N3(ii) a Molecular weight: 463.20, respectively; the elemental analysis results were: c, 85.50; h, 5.44; and N, 9.06. The reaction formula is as follows:
example 11
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 11:
(1) under nitrogen atmosphere, 9.71 g of 4-bromotriphenylamine and 15.6 g of pinacol diboron are added into a 250ml three-mouth round-bottom reaction bottle, then 240 ml of dioxane and 24 g of potassium acetate are added in turn, and the mixture is aerated and stirred for 30 minutes. Finally 700 mg of [1,1' -bis (diphenylphosphino) ferrocene are added]Palladium dichloride was introduced into the reactor for 30 minutes, heated to 85 ℃ and refluxed for 24 hours. After the reaction is stopped by cooling, the solvent of the reaction system is removed by rotary evaporation to obtain the intermediate product N, N-biphenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) aniline. The molecular formula of the product is as follows: c24H26BNO2(ii) a Molecular weight: 371.29, respectively; elemental analysis results: c, 77.64; h, 7.06; b, 2.91; n, 3.77; and O, 8.62. The reaction formula is as follows:
(2) under an atmosphere of nitrogen at 25The N, N-biphenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) aniline obtained in the previous step, 420 mg of 4-bromo-3, 5-dimethylbenzonitrile, 120ml of toluene, 40ml of anhydrous ethanol and 40ml of an aqueous solution of potassium carbonate with the concentration of 2mol/l are sequentially added into a 0ml three-neck round-bottom reaction flask, and the mixture is stirred and dissolved. After 15 minutes of aeration 50mg of tetrakis (triphenylphosphine) palladium (0) catalyst was added, and after 30 minutes of aeration, the reaction was heated to 85 ℃ and refluxed for 24 hours. And (4) after the reaction is stopped by cooling, removing the solvent of the reaction system by rotary evaporation. The reaction system was extracted with a dichloromethane solvent, and washed three times with deionized water, then three times with saturated brine, and dried over anhydrous magnesium sulfate for 1 hour. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane in a ratio of 3: 1. The final yield of the solid product was 84%. The molecular formula of the product is as follows: c27H22N2(ii) a Molecular weight: 374.18, respectively; the elemental analysis results were: c, 86.60; h, 5.92; and N, 7.48. The reaction formula is as follows:
example 12
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 12:
the difference from example 11 was that 4-bromotriphenylamine was replaced with 3-bromo-N-phenylcarbazole in equivalent amount, and the other raw materials and procedures were the same as in example 11.
(1) Intermediate 1 has the formula: c24H24BNO2(ii) a Molecular weight 369.27; elemental analysis results: c, 78.06; h, 6.55; b, 2.93; n, 3.79; o, 8.67. The reaction formula is as follows:
(2) the yield of the white solid product was finally 77%. The molecular formula of the product is as follows: c27H20N2(ii) a Molecular weight: 372.47, respectively; the elemental analysis results are: c, 87.07; h, 5.41; and N, 7.52. The reaction formula is as follows:
example 13
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 13:
under a nitrogen atmosphere, 4-bromo-3, 5-dimethylbenzonitrile (2mmol,738.54mg) and 9- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9H-carbazole (420.14mg, 2mmol) were charged into a 250mL three-necked round-bottomed reaction flask, dissolved in 120mL of toluene and 50mL of ethanol, and then dissolved in 40mL of saturated sodium carbonate solution (2mol/L) with stirring. After 15 minutes of aeration, Pd (PPh) was added rapidly3)4(150mg,0.13 mmol). After 15 minutes of aeration, the mixture was heated to 85 ℃ and refluxed with stirring for 18 hours. The reaction was stopped, and after the temperature was lowered to room temperature, the solvent was removed by rotary evaporation, extracted with a dichloromethane solvent, and washed with deionized water 3 times and then with saturated brine 3 times. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloro, and the proportion is 5: 1. the final product was 581.05mg, 78.1% yield. The molecular formula of the product is as follows: c27H20N2(ii) a Molecular weight: 372.47, respectively; elemental analysis: c, 87.07; h, 5.41; and N, 7.52. The reaction formula is as follows:
example 14
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 14:
the difference from example 12 is that 4-bromotriphenylamine is replaced by equivalent N- (4-bromophenyl) -N-phenylnaphthol-2-amine, and other raw materials and procedures are the same as in example 12.
(1) Intermediate 1 has the formula: c28H28BNO2(ii) a Molecular weight: 421.35, respectively; elemental analysis junctionAnd (4) fruit: c, 79.82; h, 6.70; b, 2.57; n, 3.32; and O, 7.59. The reaction formula is as follows:
(2) the final yield of the solid product was 76%. The molecular formula of the product is as follows: c31H24N2(ii) a Molecular weight: 424.55, respectively; the elemental analysis results were: c, 87.70; h, 5.70; and N, 6.60. The reaction formula is as follows:
example 15
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 15:
the difference from example 13 is that 9- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9H-carbazole was replaced with an equivalent amount of 3, 6-di-tert-butyl-9- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9H-carbazole, and the other starting materials and procedures were the same as in example 13. The molecular formula of the product is as follows: c35H36N2(ii) a Molecular weight: 484.69, respectively; elemental analysis results: c, 86.73; h, 7.49; n, 5.78.
Example 16
(1) Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 16:
(2) 4-bromo-3, 5-dimethylbenzonitrile (2mmol, 420.14mg) and 9,9' - (5- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1, 3-phenylene) bis (9H-carbazole) (1.18g,2.2mmol) were charged into a 250-mL three-necked round-bottomed reaction flask under a nitrogen atmosphere, 120mL of toluene and 50mL of ethanol were added and dissolved with stirring, and 40mL of a saturated potassium carbonate solution (2mol/L) was further added. Aeration for 15 minutesPost-flash addition of Pd (PPh)3)4(173.4mg, 0.15mmol) was stirred for a further 15 minutes under nitrogen. The reaction was heated to 85 degrees celsius overnight. The reaction was stopped, and after cooling to room temperature, the reaction system solvent was removed by rotary evaporation, extracted with dichloromethane solvent, and washed 3 times with deionized water. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane, and the proportion is 3: 1. the final product was 597.7mg of a white solid in 55.3% yield. The final yield of the solid product was 83%. The molecular formula of the product is as follows: c39H27N3(ii) a Molecular weight: 537.22, respectively; the elemental analysis results were: c, 87.12; h, 5.06; and N, 7.82. The reaction formula is as follows:
example 17
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 17:
compared with the example 16, the difference is that the carbazole is changed into 3, 6-di-tert-butyl-9H-carbazole with equivalent weight, and the raw materials and the steps are the same as the example 16. The final yield of the solid product was 83%. The molecular formula of the product is as follows: c55H59N3(ii) a Molecular weight: 762.10, respectively; the elemental analysis results were: c, 86.68; h, 7.80; n, 5.51. The reaction formula is as follows:
example 18
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having the structural formula 18:
(1) intermediate 1: under nitrogen atmosphere, 2.52 g (12mmol) of 4-bromo-3, 5-dimethylbenzonitrile and 2.814 g (16mmol) of 4,4,5, 5-tetramethyl-2- (3,4, 5-trifluorophenyl) -1,3, 2-dioxolane were charged into a 250-ml three-neck round-bottom reaction flask, 120ml of toluene, 50ml of ethanol, and 40ml of potassium carbonateThe saturated solution (2mol/L) was stirred. After 15 minutes of aeration, 100 mg (0.087mmol) of tetrakis (triphenylphosphine) palladium were added and aeration was continued for 15 minutes. The reaction was heated to 85 ℃ and stirred under reflux overnight. After the reaction was stopped and the temperature was reduced to room temperature, the solvent of the reaction system was removed by rotary evaporation. The reaction system was extracted with dichloromethane and washed 3 times with deionized water and three times with saturated brine. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane, and the proportion is 3: 1. 2.8 g of 3', 4',5 '-trifluoro-2, 6-dimethyl- [1,1' -biphenyl were obtained as a white solid]-4-carbonitrile (intermediate) in 89.2% yield. The molecular formula of the product is as follows: c15H10F3N; molecular weight: 261.08, respectively; elemental analysis results: c, 68.96; h, 3.86; f, 21.82; n, 5.36. The reaction formula is as follows:
(2) the final product: 671 mg (4mmol) of carbazole was added to a 250ml three-neck round-bottom reaction flask under a nitrogen atmosphere, and 50ml of N, N-dimethylformamide was added to dissolve the carbazole. To the system was added 150mg (4.5mmol) of 60% sodium hydride. After stirring for 30 minutes, 263 mg (1mol) of 3', 4',5 '-trifluoro-2, 6-dimethyl- [1,1' -biphenyl were added]Adding the 4-nitrile into a reaction bottle at one time, heating to 160 ℃, stirring, and reacting for 12 hours. The reaction was stopped, cooled to room temperature, 100 ml of water was added to the reaction flask, and a white solid appeared, which was filtered off with suction. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane, and the proportion is 1: 1, 501 mg of 3', 4',5' -tris (9H-carbazol-9-yl) -2,6 ' -dimethyl- [1,1' -biphenyl as a white solid are obtained]-4-carbonitrile in 71.4% yield. The molecular formula of the product is as follows: c51H34N4(ii) a Molecular weight: 702.86, respectively; the elemental analysis results were: c, 87.15; h, 4.88; and N, 7.97. The reaction formula is as follows:
example 19
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor units having the structural formula 19:
in comparison with example 18, the intermediate product corresponds to example 18 and is 3', 4',5 '-trifluoro-2, 6-dimethyl- [1,1' -biphenyl]4-nitrile, synthesized as in example 21. The molecular formula of the product is as follows: c15H10F3N; molecular weight: 261.08, respectively; elemental analysis results: c, 68.96; h, 3.86; f, 21.82; n, 5.36. The reaction formula is as follows:
except that carbazole was replaced by 3, 6-di-tert-butyl-9H-carbazole. Under a nitrogen atmosphere, 2.235 g (8mmol) of 3, 6-di-tert-butyl-9H-carbazole is added into a 250ml three-mouth round-bottom reaction bottle, and 50ml of N, N-dimethylformamide is added for dissolution. To the system was added 384 mg (16mmol) of 60% sodium hydride. After stirring for 30 minutes, 432.4 mg (2mol) of 3', 4',5 '-trifluoro-2, 6-dimethyl- [1,1' -biphenyl were added]Adding the 4-nitrile into a reaction bottle at one time, heating to 160 ℃, stirring, and reacting for 12 hours. The reaction was stopped, cooled to room temperature, 100 ml of water was added to the reaction flask, and a white solid appeared, which was filtered off with suction. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane, and the proportion is 1: 1.39 mg of 3'- (3- (tert-butyl) -9H-carbazol-9-yl) -4',5 '-bis (3, 6-di-tert-butyl-9H-carbazol-9-yl) -2, 6-dimethyl- [1,1' -biphenyl were finally obtained as a white solid]-4-carbonitrile in 67% yield. The molecular formula of the product is as follows: c75H82N4(ii) a Molecular weight: 1039.51, respectively; the elemental analysis results were: c, 86.66; h, 7.95; and N, 5.39. The reaction formula is as follows:
example 20
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 20:
(1) intermediate 1: 9.71 g of 9- (4-bromophenyl) -9H-3 ', 9' -dicarbazole and 15.6 g of pinacol diboron were added to a 250ml three-neck round-bottom reaction flask under nitrogen atmosphere, followed by the addition of 240 ml of dioxane followed by 24 g of potassium acetate, and the mixture was stirred for 30 minutes under aeration. Finally, 700 mg of [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium was added, and after 30 minutes of aeration, the mixture was heated to 85 ℃ and refluxed for 24 hours. After the reaction is stopped by cooling, the solvent of the reaction system is removed by rotary evaporation to obtain an intermediate product 9- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9H-3, 9' -dicarbazole. The reaction formula is as follows:
(2) the final product: in a 250ml three-mouth round bottom reaction flask, the product of the previous reaction, 9- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9H-3, 9' -dicarbazole, 420 mg of 4-bromo-3, 5-dimethyl benzonitrile, 120ml of toluene, 40ml of absolute ethanol and 40ml of aqueous solution of potassium carbonate with the concentration of 2mol/l, are sequentially added and stirred to dissolve. After 15 minutes of aeration 50mg of tetrakis (triphenylphosphine) palladium (0) catalyst was added, and after 30 minutes of aeration, the reaction was heated to 85 ℃ and refluxed for 24 hours. And (4) after the reaction is stopped by cooling, removing the solvent of the reaction system by rotary evaporation. The reaction system was extracted with a dichloromethane solvent, and washed three times with deionized water, then three times with saturated brine, and dried over anhydrous magnesium sulfate for 1 hour. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane in a ratio of 3: 1. The final yield of the solid product was 79%. The molecular formula of the product is as follows: c39H27N3(ii) a Molecular weight: 537.22, respectively; the elemental analysis results were: c, 87.12; h, 5.06; and N, 7.82. The reaction formula is as follows:
example 21
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor units having the structural formula 21:
the difference compared with example 20 is that 9- (4-bromophenyl) -9H-3 ', 9' -dicarbazole was replaced by equivalent amount of 9- (4-bromophenyl) -N, N-biphenyl-9H-carbazol-3-amine, and other raw materials and procedures were the same as in example 20.
(1) Intermediate 1 has the formula: c36H33BN2O2(ii) a Molecular weight: 536.48, respectively; elemental analysis results: c, 80.60; h, 6.20; b, 2.01; n, 5.22; and O, 5.96. The reaction formula is as follows:
(2) the final yield of the solid product was 73%. The molecular formula of the product is as follows: c39H29N3(ii) a Molecular weight: 539.24, respectively; the elemental analysis results were: c, 86.80; h, 5.42; n, 7.79. The reaction formula is as follows:
example 22
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor units having the structural formula 22:
(1) intermediate 1: under nitrogen atmosphere, 1.49 g of 9' -bromo-9 ' H-9, 3', 6 ', 9' -tricarbazole, 848.7 mg of 1-bromo-4-iodobenzene 150 ml of DMF solvent and 4.1 g of potassium carbonate were sequentially added into a 250ml three-neck round-bottom reaction flask. After stirring for 15 minutes, 100 mg of cuprous iodide catalyst was added to the system, and after 30 minutes of aeration, the mixture was heated to 120 ℃ and refluxed overnight. After the reaction was stopped by cooling, it was extracted with dichloromethane and washed with water. And (3) purifying the product by chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane in a ratio of 3: 1. The final yield of the solid product was 67%. The molecular formula of the product is as follows: c42H26BrN3(ii) a Molecular weight: 652.59, respectively; elemental analysis results: c, 77.30; h, 4.02; br, 12.24; n, 6.44. The reaction formula is as follows:
(2) intermediate 2: the remaining steps were compared to example 20 except that 9- (4-bromophenyl) -9H-3 ', 9' -dicarbazole was replaced with an equivalent amount of the product of the previous step, 9' - (4-bromophenyl) -9 ' H-9,3 ': 6 ', 9' -tricarbazole, and the other starting materials and steps were the same as in example 20. Intermediate 2 has the molecular formula: c48H38BN3O2(ii) a Molecular weight: 699.66, respectively; elemental analysis results: c, 82.40; h, 5.47; b, 1.55; n, 6.01; and O, 4.57. The reaction formula is as follows:
(3) the final yield of the solid product was 75%. The molecular formula of the product is as follows: c51H34N4(ii) a Molecular weight: 702.86, respectively; the elemental analysis results were: c, 87.15; h, 4.88; and N, 7.97. The reaction formula is as follows:
example 23
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit having structural formula 23:
the difference from example 22 was that 9 '-bromo-9' H-9,3 ': 6', 9 '-tricarbazole was replaced with an equivalent amount of 9' -bromo-3, 3', 6, 6' -tetra-tert-butyl-phenyl-9 'H-9, 3': 6 ', 9' -tricarbazole, and the other raw materials and procedures were the same as in example 22.
(1) Intermediate 1 has the formula: c58H58BrN3(ii) a Molecular weight: 877.03, respectively; elemental analysis results: c, 79.43; h, 6.67; br, 9.11; n, 4.79. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c64H70BN3O2(ii) a Molecular weight: 924.09, respectively; elemental analysis results: c, 83.18; h, 7.64; b, 1.17; n, 4.55; and O, 3.46. The reaction formula is as follows:
(3) the final yield of the solid product was 78%. The molecular formula of the product is as follows: c67H66N4(ii) a Molecular weight: 927.29, respectively; the elemental analysis results were: c, 86.78; h, 7.17; and N, 6.04. The reaction formula is as follows:
example 24
Preparation of a 2, 6-dimethyl-4-benzonitrile acceptor unit-based small organic molecule material having structural formula 24:
the difference from example 22 was that 9' -bromo-9 ' H-9, 3', 6 ', 9' -tricarbazole was replaced with an equivalent amount of N3, N3, N6, N6-tetraphenyl-9H-carbazole-3, 6-diamine, and the other starting materials and procedures were the same as in example 22.
(1) Intermediate 1 has the formula: c42H30BrN3(ii) a Molecular weight: 656.63, respectively; elemental analysis results: c, 76.83; h, 4.61; br, 12.17; and N, 6.40. The reaction formula is as follows:
(2) intermediate 2 has the molecular formula: c48H42BN3O2(ii) a Molecular weight: 703.69, respectively; elemental analysis results: c, 81.93; h, 6.02; b, 1.54; n, 5.97; and O, 4.55. The reaction formula is as follows:
(3) the final yield of the solid product was 78%. The molecular formula of the product is as follows: c51H38N4(ii) a Molecular weight: 706.31, respectively; the elemental analysis results were: c, 86.66; h, 5.42; and N, 7.93. The reaction formula is as follows:
example 25
Preparation of a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor units having the structural formula 25:
(1) intermediate 1 (I)2CzTBS) in a nitrogen atmosphere, 12.74g (30.4mmol) of 3, 6-dibromo-9H-carbazole was charged into a 250-ml three-necked round-bottomed reaction flask, and 100 ml of N, N-dimethylformamide was added to dissolve the carbazole, followed by cooling to 0 ℃. 1500 mg (45mmol) of 60% sodium hydride are slowly added and stirred for 30 minutes. 4590 mg (36.43mmol) of t-butyldimethylsilyl chloride was added to the reaction system at a time, and stirred for 1 hour. After the temperature had risen to room temperature, stirring was continued for two hours. After the reaction was complete, the mixture was extracted three times with toluene solution and the organic phase was spin dried to give a white solid. Purifying the product by column chromatography, wherein the eluent is a mixed solution of toluene and n-hexane in a ratio of 1: 2. The white solid (I) is finally obtained2CzTBS). Molecular formula C18H21I2NSi, respectively; molecular weight: 533.96, respectively; elemental analysis results: c, 40.54; h, 3.97; and N, 2.63. The reaction formula is as follows:
(2) intermediate 2: 6.44 g of carbazole (38.5mmol), 10 g of I were added to a 250ml three-neck round-bottom reaction flask under a nitrogen atmosphere2CzTBS (18.8mol), 364 mg of CuI (1.91mmol) and 24.3 gK3PO4(114mmol), 160 ml of dioxane was added and dissolved, and 338. mu.l of (. + -.) -trans-1, 2-cyclohexanediamine (2.81mmol) were added. Heating to 110 ℃, stirring and reacting for 15 hours. And (4) stopping the reaction, cooling to room temperature, and then spin-drying the solvent of the reaction system. Purifying the product by column chromatography, wherein an eluent is a mixed solution of toluene and n-hexane in a ratio of 1: 2. intermediate 2 was finally obtained as a white solid. The molecular formula of the product is C42H37N3Si; molecular weight 611.28; elemental analysis results: c, 82.19; h, 6.42; n, 6.92. The reaction formula is as follows:
(3) intermediate 3: intermediate 2 was added to the single-neck flask, dissolved in 50ml of toluene, and then 24.8 ml of a tetrahydrofuran solution (1M) of tetrabutylammonium fluoride was added thereto, and stirred for 15 minutes. Adding ammonium chloride solution into the system, and separating the phases. The organic phase was obtained by extraction three times with toluene and spin drying. Dissolving the solid in a small amount of toluene solution, adding n-hexane, and recrystallizing. Finally obtaining intermediate product 9 'H-9, 3' 6 ', 9' -tricarbazole. The molecular formula of the product is as follows: c36H23N3(ii) a Molecular weight: 497.60, respectively; elemental analysis results: c, 86.90; h, 4.66; n, 8.44.
The reaction formula is as follows:
(4) intermediate 4: compared with the reaction of the intermediate product 2, the difference is that carbazole is replaced by equivalent 9 'H-9, 3' to 6 ', 9' -tricarbazole, and the rest of reaction steps and the reaction of the intermediate product 2 between the raw materials are carried out. The molecular formula of the product is as follows: c90H65N7Si; molecular weight: 1272.64, respectively; elemental analysis results: c, 84.94; h, 5.15; n, 7.70; si, 2.21. The reaction formula is as follows:
(5) intermediate 5: the reaction is completely consistent with the steps and raw materials of the intermediate product 3, and the specific steps are shown in the reaction 3. The molecular formula of the product is as follows: c84H51N7(ii) a Molecular weight: 1158.38, respectively; elemental analysis results: c, 87.10; h, 4.44; and N, 8.46. The reaction formula is as follows:
(6) the final product: 1868 mg (1.61mmol) of 6 ', 6' -bis (9H-carbazol-9-yl) -9 'H-9, 3': 9', 3': 6 ', 9': 3', 9' pentacarbazole was added to a 250-ml three-necked round-bottomed reaction flask under a nitrogen atmosphere, and 150 ml of N, N-dimethylformamide was added to dissolve the mixture. To the system was added 100 mg (3mmol) of 60% sodium hydride. After stirring for 30 minutes, 362.5 mg (1.61mmol) of 4 '-fluoro-2, 6-dimethyl- [1,1' -biphenyl were added]Adding the 4-nitrile into a reaction bottle at one time, heating to 160 ℃, stirring, and reacting for 12 hours. The reaction was stopped, cooled to room temperature, 100 ml of water was added to the reaction flask, and a white solid appeared, which was filtered off with suction. Purifying the product by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and dichloromethane, and the proportion is 1: 1 to yield 1545.6 mg of a white solid 4' - (6 ', 6 ' -bis (9H-carbazol-9-yl) -9 ' H-9,3 ': 9', 3 ': 6 ', 9 ': 3', 9' -pentacarbazole]-9 "-yl) -2, 6-dimethyl- [1,1' -biphenyl]-4-carbonitrile in a yield of 70.4%. The molecular formula of the product is as follows: c99H62N8(ii) a Molecular weight: 1363.64, respectively; the elemental analysis results were: c, 87.20; h, 4.58; and N, 8.22. The reaction formula is as follows:
example 26
This example prepares an organic electroluminescent device (device 1) having DPEPO as the main component, and the specific stacked structure is as follows:
glass substrate/ITO/TAPC/mCP/SPDMAc-TRZ DPEPO/DPEPO/TmPyPB/LiF/Al. ITO as anode, TAPC as hole injection layer, mCP as electron and hole blocking layer, DPEPO as electron and hole blocking layer, TmPyPB as electron transport layer, LiF as electron injection layer, Al as cathode.
The preparation method of the organic electroluminescent device comprises the following steps: and ultrasonically cleaning the ITO transparent conductive glass for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into a thermostat to be dried at 80 ℃ for later use. The dried ITO substrate was treated with an oxygen plasma glow starter for 3 minutes to remove organic deposits on the surface. The glass with the anode ITO is placed in a vacuum chamber under the vacuum condition of 1 multiplied by 10-5～9×10- 3At Pa, in
The deposition rate of (2) is to evaporate an organic material layer on the anode film, wherein in the evaporation of a luminous layer, the luminous material and the main material are respectively placed on two evaporation sources, and the mixing ratio of the luminous material and the main material is controlled by a certain deposition rate. Then is followed by
Evaporating LiF at a deposition rate of
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
Example 27
This example prepares an organic electroluminescent device (device 2) based on a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit of formula 18 as the host, and the specific stacked structure is as follows:
glass substrate/ITO/TAPC/mCP/SPDMAc-TRZ: 18/DPEPO/TmPyPB/LiF/Al. ITO as anode, TAPC as hole injection layer, mCP as electron and hole blocking layer, DPEPO as electron and hole blocking layer, TmPyPB as electron transport layer, LiF as electron injection layer, Al as cathode.
The preparation method of the organic electroluminescent device comprises the following steps: and ultrasonically cleaning the ITO transparent conductive glass for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into a thermostat to be dried at 80 ℃ for later use. The dried ITO substrate was treated with an oxygen plasma glow starter for 3 minutes to remove organic deposits on the surface. The glass with the anode ITO is placed in a vacuum chamber under the vacuum condition of 1 multiplied by 10-5～9×10- 3At Pa, in
The deposition rate of (2) is to evaporate an organic material layer on the anode film, wherein in the evaporation of a luminous layer, the luminous material and the main material are respectively placed on two evaporation sources, and the mixing ratio of the luminous material and the main material is controlled by a certain deposition rate. Then is followed by
Evaporating LiF at a deposition rate of
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
Example 28
This example prepares an organic electroluminescent device (device 3) based on a small organic molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit of formula 18 as the host, and the specific stacked structure is as follows:
glass substrate/ITO/TAPC/mCP/SPDMAc-TRZ: 18/TmPyPB/LiF/Al. ITO as anode, TAPC as hole injection layer, mCP as electron blocking layer and hole transport layer, TmPyPB as electron transport layer, LiF as electron injection layer, Al as cathode.
The preparation method of the organic electroluminescent device comprises the following steps: the ITO transparent conductive glass is sequentially cleaned by acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol for 15 minutes in an ultrasonic mode to remove dirt on the surface of the substrateAnd (4) scale formation. And then putting the mixture into a thermostat to be dried at 80 ℃ for later use. The dried ITO substrate was treated with an oxygen plasma glow starter for 3 minutes to remove organic deposits on the surface. The glass with the anode ITO is placed in a vacuum chamber under the vacuum condition of 1 x 10 < -5 > to 9 x 10 < -3 > Pa to
The deposition rate of (2) is to evaporate an organic material layer on the anode film, wherein in the evaporation of a luminous layer, the luminous material and the main material are respectively placed on two evaporation sources, and the mixing ratio of the luminous material and the main material is controlled by a certain deposition rate. Then is followed by
Evaporating LiF at a deposition rate of
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
The structural formulas of the materials used in the above examples 26 to 28 are as follows:
the current density-voltage-luminance relationship graph, the current efficiency-luminance-power efficiency relationship graph, the external quantum efficiency-luminance relationship graph, and the electroluminescence spectrum of the organic electroluminescent devices obtained in examples 26 to 28 are shown in fig. 1,2, 3, and 4, respectively. The basic characterization data of the comparison of the service life of the organic electroluminescent device made of the organic small molecule material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit with the structural formula 18 and DPEPO are shown in Table 1.
TABLE 1
The results show that the organic small molecular material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit has better photoelectric property and obviously prolonged service life compared with a device obtained by DPEPO.
The fluorescence spectrum and phosphorescence spectrum of the 2, 6-dimethyl-4-cyanophenyl acceptor unit-based organic small molecule material having the structural formula 18 used in the above examples 27 to 28 under the pure film condition are shown in fig. 5.
FIG. 6 shows the fluorescence spectrum and phosphorescence spectrum of the luminescent guest compound SPDMAc-TRZ used in examples 26-28 in the presence of a toluene solution.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. An organic small molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit, characterized in that the organic small molecule material has a structural formula shown in formula (I):
wherein Ar represents a phenyl aromatic amine heterocycle or a phenyl aromatic amine donor unit represented by any one of (1) to (25):
2. the preparation method of the organic small molecule material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit as claimed in claim 1 is characterized in that the preparation method comprises the following steps: the intermediate shown in the formula (II) is prepared by Suzuki or Buchwald-Hartwig coupling reaction,
3. the use of the organic small molecule material based on 2, 6-dimethyl-4-benzonitrile acceptor unit as claimed in claim 1 in organic opto-electronic devices.
4. The application of the organic small molecule material based on the 2, 6-dimethyl-4-benzonitrile acceptor unit in the organic photoelectric device as claimed in claim 3, wherein: the organic photoelectric device comprises a substrate, an anode layer, a plurality of organic functional layer units and a cathode layer, wherein the anode layer, the plurality of organic functional layer units and the cathode layer are sequentially formed on the substrate; the organic functional layer unit comprises a hole injection layer, a hole transport layer, one or more light emitting layers and an electron transport layer; the preparation material of the light-emitting layer comprises one or more than two of the organic small molecule materials based on the 2, 6-dimethyl-4-cyanophenyl acceptor unit in claim 1.
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| Title |
|---|
| Efficient and tunable thermally activated delayed fluorescence emitters having orientation-adjustable CN-substituted pyridine and pyrimidine acceptor units;Kuan-chung Pan 等;《Advanced functional materials》;20160905;第26卷;第7560-7571页 * |
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