CN114426558B - Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device - Google Patents
Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device Download PDFInfo
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- CN114426558B CN114426558B CN202210145745.1A CN202210145745A CN114426558B CN 114426558 B CN114426558 B CN 114426558B CN 202210145745 A CN202210145745 A CN 202210145745A CN 114426558 B CN114426558 B CN 114426558B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000010410 layer Substances 0.000 claims description 106
- 239000012044 organic layer Substances 0.000 claims description 19
- 150000001923 cyclic compounds Chemical class 0.000 claims 1
- 239000011669 selenium Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 229910052711 selenium Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052714 tellurium Inorganic materials 0.000 abstract description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005281 excited state Effects 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 210
- 238000006243 chemical reaction Methods 0.000 description 189
- 239000000203 mixture Substances 0.000 description 124
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 99
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 98
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 92
- 238000004458 analytical method Methods 0.000 description 79
- 239000012300 argon atmosphere Substances 0.000 description 79
- 238000003795 desorption Methods 0.000 description 79
- 238000000921 elemental analysis Methods 0.000 description 79
- 239000011159 matrix material Substances 0.000 description 79
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 79
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 54
- 239000012043 crude product Substances 0.000 description 53
- 239000012074 organic phase Substances 0.000 description 52
- 229920006395 saturated elastomer Polymers 0.000 description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 50
- 239000000741 silica gel Substances 0.000 description 50
- 229910002027 silica gel Inorganic materials 0.000 description 50
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 49
- 235000019270 ammonium chloride Nutrition 0.000 description 49
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 46
- 239000000047 product Substances 0.000 description 46
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 44
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 27
- 238000001914 filtration Methods 0.000 description 26
- -1 but not limited to Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 21
- FCDNEESKPPIAJZ-UHFFFAOYSA-N bis[3,5-di(carbazol-9-yl)phenyl]-diphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 FCDNEESKPPIAJZ-UHFFFAOYSA-N 0.000 description 20
- 238000007738 vacuum evaporation Methods 0.000 description 18
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 238000010129 solution processing Methods 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 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 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 125000004429 atom Chemical group 0.000 description 5
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-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
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000005885 boration reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
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- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000006749 (C6-C60) aryl group Chemical group 0.000 description 1
- VYKNVAHOUNIVTQ-UHFFFAOYSA-N 1,2,2,3,3-pentamethylpiperidine Chemical compound CN1CCCC(C)(C)C1(C)C VYKNVAHOUNIVTQ-UHFFFAOYSA-N 0.000 description 1
- KBGPFZUZKTUOII-UHFFFAOYSA-N 1,3,6,8-tetramethyl-9h-carbazole Chemical compound C1=C(C)C=C2C3=CC(C)=CC(C)=C3NC2=C1C KBGPFZUZKTUOII-UHFFFAOYSA-N 0.000 description 1
- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
- C09K2211/107—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms with other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a condensed-ring compound containing three boron atoms, a preparation method thereof and an electroluminescent device, belonging to the technical field of organic luminescent materials. The condensed-cyclic compound has a structure shown in a formula (I). The fused ring compound is characterized in that three boron atoms and electron-rich atoms (oxygen, nitrogen, sulfur, selenium and tellurium) are embedded in a fused ring molecular skeleton, the resonance effect between the boron atoms and donor atoms (oxygen, nitrogen, sulfur, selenium and tellurium) is utilized to realize the separation of HOMO and LUMO, so that the smaller delta E ST and TADF effects are realized, and meanwhile, the rigid skeleton structure of the fused ring compound can reduce the relaxation degree of an excited state structure, so that the narrower half-peak width is realized. The fused ring compound provided by the invention is used as a light-emitting layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized without a filter and a microcavity structure, but also the high external quantum efficiency of the device can be realized. The preparation method provided by the invention has the advantages of mild conditions and higher product yield.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a condensed-cyclic compound containing three boron atoms, a preparation method thereof and an electroluminescent device.
Background
Organic Light Emitting Devices (OLEDs) are typically composed of a cathode, an anode and organic layers interposed between the cathode and anode, i.e., the device is composed of a transparent ITO anode, a hole injection layer (TIL), a Hole Transport Layer (HTL), a light Emitting Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and a cathode, and 1 to 2 organic layers may be omitted or an Exciton Blocking Layer (EBL) may be added as needed. The action mechanism is that voltage is formed between the two electrodes, electrons are injected from the cathode and holes are injected from the anode at the same time, the electrons and the holes are combined in the light-emitting layer to form an excited state, and the excited state is radiated back to the ground state, so that the light emission of the device is realized. Due to the characteristics of rich colors, quick response, capability of preparing flexible devices and the like, the organic electroluminescent material is considered as the next generation flat panel display and solid illumination material with the most development prospect.
However, due to the limitation of the statistical law of spin quanta, the traditional fluorescent material can only utilize 25% of singlet excitons in the electroluminescence process, 75% of triplet excitons are lost in a non-radiative transition form, and the theoretical limit value of the quantum efficiency (IQE) in the device is 25%. Thus, fully utilizing triplet excitons is one of the effective ways to increase quantum efficiency. For example, phosphorescent metal complexes can convert triplet excitons into photons using orbital coupling of heavy metal atoms, achieving 100% internal quantum efficiency. However, this approach faces the problem of expensive phosphorescent metal complexes. Another approach to utilizing triplet excitons is to develop luminescent materials with Thermally Activated Delayed Fluorescence (TADF) properties that are capable of converting triplet excitons to singlet states using a thermally activated reverse intersystem crossing (RISC) process and quenching into the ground state to fluoresce by radiation, thereby achieving full utilization of singlet and triplet excitons without the need for precious metals.
The main approach in designing TADF materials is to introduce donor (D) and acceptor (a) groups so that the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) can be spatially separated effectively, thereby realizing a small singlet-triplet energy level difference (Δe ST) and promoting the trans-intersystem crossing process. However, since the excited state of the D-A structure shows strong vibrational relaxation, the luminescence spectrum is wide, and the full width at half maximum (FWHM) is generally 70-100nm, resulting in poor color purity. In practical applications, a filter or an optical microcavity is often required to be used to improve the color purity, but this may lead to a decrease in the external quantum efficiency of the device or a complicated device structure.
Therefore, how to solve the defect of wider half-peak width faced by the above materials by proper chemical structure design, developing TADF fluorescent materials with narrow spectral characteristics has become one of the problems to be solved by many researchers in the field.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a condensed-cyclic compound containing three boron atoms, a preparation method thereof and an electroluminescent device. The fused ring compound provided by the invention is characterized in that three boron atoms and electron-rich atoms (oxygen, nitrogen, sulfur, selenium and tellurium) are embedded in a fused ring molecular skeleton, and the separation of HOMO and LUMO is realized by utilizing the resonance effect between the boron atoms and donor atoms (oxygen, nitrogen, sulfur, selenium and tellurium), so that the smaller delta E ST and TADF effects are realized, and meanwhile, the fused ring compound has a rigid skeleton structure capable of reducing the relaxation degree of an excited state structure, so that the narrower half-peak width is realized. The fused ring compound provided by the invention is used as a light-emitting layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized without a filter and a microcavity structure, but also the high external quantum efficiency of the device can be realized.
In order to solve the technical problems, the technical scheme of the invention is as follows:
The invention provides a condensed-cyclic compound containing three boron atoms, which has a structure shown in a formula (I):
wherein, X 1 and X 2 are each independently selected from N (R 1), O, S, se or Te;
each independently selected from a C6 to C60 aryl ring, or a C3 to C60 heteroaryl ring;
R 1～R7 is independently selected from H, D, F, cl, br, I, -CN, -CF 3, C1-C30 straight chain hydrocarbon group, C3-C30 branched chain hydrocarbon group, C3-C30 cycloalkyl group, C1-C30 alkoxy group, C1-C30 alkylthio group, C6-C60 aryl ether group, C3-C60 heteroaryl group or C3-C60 heteroaryl ether group; wherein the heteroatoms of the heteroaromatic groups are independently selected from Si, ge, N, P, O, S or Se;
n 1～n7 is independently selected from integers from 0 to 4;
R 1 is selected from H, D, C to C30 straight-chain hydrocarbon, C3 to C30 branched-chain hydrocarbon, C3 to C30 cycloalkyl, C6 to C60 aryl or C3 to C60 heteroaryl; the heteroatoms of the heteroaryl groups are independently selected from Si, ge, N, P, O, S or Se.
In the above technical solution, it is preferable that: the saidAndCan also be connected with any one of- (SO 2) -by a single bond 、-C(R1R2)-、-(C＝O)-、-Si(R1R2)-、-N(R1)-、-B(R1)-、-PO(R1)-、-O-、-S-、-Se-、-(S＝O)-;
wherein R 1 and R 2 are each independently selected from the group consisting of a straight chain hydrocarbon group of H, D, C to C30, a branched chain hydrocarbon group of C3 to C30, a cycloalkyl group of C3 to C30, an aryl group of C6 to C60, and a heteroaryl group of C3 to C60; the heteroatoms of the heteroaryl groups are independently selected from Si, ge, N, P, O, S or Se.
In the above technical solution, it is preferable that: the saidEach independently selected from the following structures:
L 1～L10 is independently selected from the group consisting of C1-C30 straight-chain hydrocarbon groups, C3-C30 branched-chain hydrocarbon groups, C1-C30 haloalkyl groups, C3-C30 cycloalkyl groups, C6-C60 aromatic groups, and C5-C60 heteroaromatic groups; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se.
In the above technical solution, most preferred is: the fused ring compound containing three boron atoms is selected from one of the following structures:
The invention also provides a preparation method of the condensed-cyclic compound containing three boron atoms, which comprises the following steps:
Mixing a precursor with a structure shown in a formula (X), a boration reagent and an organic solvent in a protective atmosphere, and reacting to obtain a condensed-cyclic compound containing three boron atoms shown in a formula (I);
the definition of each substituent group and the number thereof in the structural formula are defined as the formula (I).
In the above technical solution, it is preferable that: the boration reagent is one or more of boron trifluoride, boron trichloride, boron triiodide and boron tribromide; the organic solvent is one or more of toluene, dimethylbenzene, chlorobenzene, o-dichlorobenzene and 1,2, 4-trichlorobenzene.
In the above technical solution, it is preferable that: the protective atmosphere comprises nitrogen and/or inert gas.
In the above technical solution, it is preferable that: the temperature of the reaction is 90-180 ℃, and the time of the reaction is 20-30 hours, more preferably 24 hours.
In the above technical solution, it is preferable that: in order to increase the reaction yield, a base may be added based on the above reaction conditions, the base including one or more of N, N-diisopropylethylamine, triethylamine, 2, 6-tetramethylpiperidine, pentamethylpiperidine, 2, 6-lutidine and N, N-dimethyl-p-toluidine.
The invention also provides an organic electroluminescent device comprising an anode, a cathode and an organic layer positioned between the anode and the cathode; the organic layer includes a light emitting layer; the light-emitting layer comprises a condensed ring compound containing three boron atoms and represented by the formula (I) of the present invention.
The structure of the organic electroluminescent device is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the application situation, quality requirements and product requirements by using a conventional organic electroluminescent device well known to the person skilled in the art, and the structure of the organic electroluminescent device preferably comprises:
A substrate; an anode disposed on the substrate; an organic layer disposed on the anode;
Wherein the number of the organic layers is preferably more than or equal to 1, and at least one of the organic layers is preferably an organic electroluminescent layer; the organic electroluminescent layer preferably comprises one or more condensed-cyclic compounds containing three boron atoms represented by the formula (I) of the present invention;
And a cathode disposed on the organic layer.
The choice of the substrate according to the invention is not particularly limited, but can be selected and adjusted by a person skilled in the art according to the application, quality requirements and product requirements, with the substrate according to the invention preferably being glass or plastic, as is known to a person skilled in the art for conventional organic electroluminescent devices. The thickness of the substrate is preferably 0.3 to 0.7mm, more preferably 0.4 to 0.6mm.
According to the invention, the anode is preferably a material that is prone to hole injection, more preferably a conductive metal or conductive metal oxide, and more particularly preferably indium tin oxide.
The organic layer can be 1 layer or multiple layers, and at least one layer of the organic layers is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more condensed ring compounds containing three boron atoms and shown in the formula (I). The condensed-cyclic compound containing three boron atoms represented by the formula (I) of the present invention preferably constitutes an organic electroluminescent layer directly as a light-emitting material.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
The organic layer between the anode and the organic electroluminescent layer preferably further comprises one or more of a hole injection layer, a hole transport layer and an electron blocking layer in order to improve the performance and efficiency of the device. The organic layer between the organic electroluminescent layer and the cathode preferably further includes one or more of a hole blocking layer and an electron injection layer and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the process of preparing the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer, and preferably, the present invention is prepared by using processes of vacuum evaporation, solution spin coating, solution doctor blading, inkjet printing, offset printing and three-dimensional printing.
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method:
Forming an anode on the substrate; forming one or more organic layers on the anode, including an organic electroluminescent layer; forming a cathode on the organic layer;
the organic electroluminescent layer comprises one or more condensed ring compounds containing three boron atoms and represented by the formula (I).
The structure and the materials of the organic electroluminescent device and the corresponding preferred principles of the preparation method of the invention can correspond to the corresponding materials and structures of the organic electroluminescent device and the corresponding preferred principles, and are not described in detail herein.
The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. The method of forming the organic layers below and above the organic electroluminescent layer and the light-emitting layer is not particularly limited, and the organic layers may be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited as to the manner of forming the cathode after the organic layer is formed, and is preferably a method known to those skilled in the art, including but not limited to vacuum deposition, to prepare the cathode on the surface thereof.
The beneficial effects of the invention are as follows:
The fused ring compound containing three boron atoms is characterized in that three boron atoms and electron-rich atoms (oxygen, nitrogen, sulfur, selenium and tellurium) are embedded in a fused ring molecular skeleton, and the resonance effect between the boron atoms and donor atoms (oxygen, nitrogen, sulfur, selenium and tellurium) is utilized to realize the separation of HOMO and LUMO, so that the smaller delta E ST and TADF effects are realized, and meanwhile, the fused ring compound has a rigid skeleton structure capable of reducing the relaxation degree of an excited state structure, so that the narrower half-peak width is realized. Experimental results show that the fused ring compound provided by the invention is used as a light-emitting layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized without a filter and a microcavity structure, but also the high external quantum efficiency of the device can be realized.
The preparation method of the fused ring compound containing three boron atoms provided by the invention has the advantages of mild conditions and higher product yield.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the condensed-cyclic compound containing three boron atoms, the preparation method thereof and the organic electroluminescent device in detail, but they should not be construed as limiting the scope of the present invention.
The reagents used in the examples below are all commercially available.
Example 1
The reaction formula is as follows:
1-1 (13.0 g,40.0 mmol), 1-2 (5.2 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butyl phosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium tert-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give the product 1-3 (14.2 g, yield: 95%).
Elemental analysis structure (C 54H42N4): theoretical value C,86.83; h,5.67; n,7.50; experimental value C,86.81; h,5.65; n,7.54.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 746.3; experimental value 746.3 (M +).
1-3 (3.7 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 20mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The temperature was lowered to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give product A-1-1 (2.3 g, yield: 60%).
Elemental analysis structure (C 54H33B3N4): theoretical C,84.20; h,4.32; n,7.27; experimental value C,84.19; h,4.35; n,7.23.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 770.3; experimental value 771.3 ([ M+H ] +).
The photophysical properties of the fused ring compound prepared in example 1 of the present invention were examined, and the results are shown in Table 1.
Example 2
The reaction formula is as follows:
in a 100mL two-necked flask, m-phenylenediamine (2.2 g,20.0 mmol), 2-bromonaphthalene (8.3 g,40.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (560.1 mg,0.9 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 40mL anhydrous toluene were charged under argon atmosphere, and the reaction was stirred at 110℃for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 2-1 (6.5 g, yield: 90%).
Elemental analysis structure (C 26H20N2): theoretical value C,86.64; h,5.59; n,7.77; experimental C,86.63; h,5.60; n,7.78.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 360.2; experimental 360.2. (M +).
1-1 (13.0 G,40.0 mmol), 2-1 (7.2 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 2-2 (15.2 g, yield: 90%).
Elemental analysis structure (C 62H46N4): theoretical value C,87.91; h,5.47; n,6.61; experimental C,87.89; h,5.48; n,6.64.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 846.4; experimental values 846.4. (M +).
2-2 (4.3 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The temperature was lowered to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product A-3-1 (2.4 g, yield: 55%).
Elemental analysis structure (C 62H37B3N4): theoretical value C,85.55; h,4.28; n,6.44; experimental value C,85.56; h,4.25; n,6.42.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 870.3; experimental value 871.3 ([ M+H ] +).
The photophysical properties of the fused ring compound prepared in example 2 of the present invention were examined, and the results are shown in Table 1.
Example 3
The reaction formula is as follows:
3-1 (5.0 g,20.0 mmol), 3-2 (7.3 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (275.0 mg,0.3 mmol), 1' -bis (diphenylphosphino) ferrocene (332.6 mg,0.6 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and 40mL anhydrous toluene were added to a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 20 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 3-3 (6.2 g, yield: 85%).
Elemental analysis structure (C 20H14 BrNO): theoretical value C,65.95; h,3.87; n,3.85; experimental value C,65.94; h,3.86; n,3.87.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 363.0; experimental value 363.0 (M +).
3-3 (14.6 G,40.0 mmol), 1-2 (7.3 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butyl phosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium tert-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 3-4 (15.2 g, yield: 92%).
Elemental analysis structure (C 58H42N4O2): theoretical C,84.24; h,5.12; n,6.77; experimental value C,84.21; h,5.10; n,6.80.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 826.3; experimental value 826.3 (M +).
3-4 (4.1 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 20mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give product A-7-2 (2.4 g, yield: 57%).
Elemental analysis structure (C 58H33B3N4O2): theoretical value C,81.92; h,3.91; n,6.59; experimental value C,81.94; h,3.90; n,6.61.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 850.4; experimental value 851.4 ([ M+H ] +).
The photophysical properties of the fused ring compound prepared in example 3 of the present invention were examined, and the results are shown in Table 1.
Example 4
The reaction formula is as follows:
4-1 (22.3 g,60.0 mmol), 4-2 (6.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were placed in a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 4-3 (14.4 g, yield: 87%).
Elemental analysis structure (C 54H41BrN4): theoretical value C,78.54; h,5.00; n,6.78; experimental value C,78.57; h,4.98; n,6.76.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 824.3; experimental value 825.3 ([ M+H ] +).
4-3 (16.5 G,20.0 mmol), 3, 6-di-tert-butylcarbazole (5.6 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tris-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and 100mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 4-4 (18.4 g, yield: 90%).
Elemental analysis structure (C 74H65N5): theoretical value C,86.77; h,6.40; n,6.84; experimental value C,86.75; h,6.39; n,6.82.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1023.5; experimental value 1023.5 (M +).
4-4 (5.1 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 20mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product A-17-4 (3.7 g, yield: 68%).
Elemental analysis structure (C 76H64B3N5): theoretical value C,84.54; h,5.97; n,6.49 experimental value C84.52; h,5.96; n,6.45.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1079.5; experimental value 1079.5 (M +).
The photophysical properties of the fused ring compound prepared in example 4 of the present invention were examined, and the results are shown in Table 1.
Example 5
The reaction formula is as follows:
5-1 (14.4 g,40.0 mmol), 5-2 (6.0 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 100mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give a product 5-3 (16.0 g, yield: 93%).
Elemental analysis structure (C 57H46Cl2N4): theoretical value C,79.80; h,5.40; n,6.53; experimental value C,79.84; h,5.39; n,6.52.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 856.3; experimental value 857.3 ([ M+H ] +).
5-3 (17.2 G,20.0 mmol), 5-4 (9.0 g,40.0 mmol), NECO-296 (1.5 g,2.4 mmol), sodium t-butoxide (11.5 g,120.0 mmol) and 150mL of anhydrous mesitylene were placed in a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 130℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give a product 5-5 (17.3 g, yield: 70%).
Elemental analysis structure (C 89H82N6): theoretical value C,86.51; h,6.69; n,6.80; experimental value C,86.50; h,6.70; n,6.78.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1234.7; experimental value 1234.7 (M +).
5-5 (6.2 G,5.0 mmol), boron triiodide (11.8 g,30.0 mmol) and 20mL of 1,2, 4-trichlorobenzene were placed in a 100mL two-necked flask under argon atmosphere, and the temperature was raised to 90℃and the mixture was stirred for 24 hours. The temperature was lowered to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product A-17-10 (3.2 g, yield: 50%).
Elemental analysis structure (C 89H73B3N6): theoretical value C,84.90; h,5.84; n,6.68 experimental value C84.88; h,5.85; n,6.66.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1258.6; experimental value 1258.6 (M +).
The photophysical properties of the fused ring compound prepared in example 5 of the present invention were examined, and the results are shown in Table 1.
Example 6
The reaction formula is as follows:
6-1 (7.3 g,20.0 mmol), 5-2 (9.1 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 40mL of anhydrous toluene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 6-2 (9.4 g, yield: 80%).
Elemental analysis structure (C 42H41N3): theoretical value C,85.82; h,7.03; n,7.15; experimental value C,85.80; h,7.01; n,7.13.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 587.3; experimental value 588.3 ([ M+H ] +).
6-2 (11.8 G,20.0 mmol), 6-3 (5.0 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 6-4 (13.9 g, yield: 92%).
Elemental analysis structure (C 55H49N3 O) theoretical value C,85.79; h,6.53; n,5.56; experimental value C,85.77; h,6.54; n,5.55.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 755.4; experimental value 755.4 (M +).
6-4 (3.8 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 20mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product B-6-1 (2.3 g, yield: 60%).
Elemental analysis structure (C 54H40B3N3 O): theoretical value C,83.22; h,5.17; n,5.39; experimental value C,83.24; h,5.16; n,5.40.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 779.4; experimental value 779.4 (M +).
The photophysical properties of the fused ring compound prepared in example 6 of the present invention were examined, and the results are shown in Table 1.
Example 7
The reaction formula is as follows:
1-1 (6.5 g,20.0 mmol), 7-1 (9.9 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 40mL of anhydrous toluene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 7-2 (8.6 g, yield: 75%).
Elemental analysis structure (C 36H27Cl2N3): theoretical C,75.52; h,4.75; n,7.34; experimental value C,75.50; h,4.74; n,7.36.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 571.2; experimental value 572.2 ([ M+H ] +).
7-2 (11.5 G,20.0 mmol), 6-3 (5.0 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 7-3 (13.5 g, yield: 91%).
Elemental analysis structure (C 48H35Cl2N3 O): theoretical C,77.83; h,4.76; n,5.67; experimental value C,77.80; h,4.77; n,5.65.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 739.2; experimental value 740.2 ([ M+H ] +).
7-3 (11.5 G,20.0 mmol), 3, 6-di-tert-butylcarbazole (11.2 g,40.0 mmol), NECO-296 (1.5 mg,2.4 mmol), sodium tert-butoxide (11.5 g,120.0 mmol) and 150mL of anhydrous mesitylene were put into a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 130℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 7-4 (18.2 g, yield: 74%).
Elemental analysis structure (C 88H83N5 O): theoretical value C,86.17; h,6.82; n,5.71; experimental value C,86.11; h,6.81; n,5.70.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1225.7; experimental value 1225.7 (M +).
7-4 (6.1 G,5.0 mmol), boron triiodide (11.8 g,30.0 mmol) and 20mL of 1,2, 4-trichlorobenzene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 90℃and stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product B-6-3 (3.4 g, yield: 55%).
Elemental analysis structure (C 88H74B3N5 O): theoretical value C,84.56; h,5.97; n,5.60; experimental value C,84.59; h,5.96; n,5.58.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1249.6; experimental value 1249.6 (M +).
The photophysical properties of the fused ring compound prepared in example 7 of the present invention were examined, and the results are shown in Table 1.
Example 8
The reaction formula is as follows:
Into a 250mL two-necked flask, 8-1 (9.0 g,20.0 mmol), 8-2 (12.0 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL anhydrous toluene were charged under an argon atmosphere, and the reaction was stirred at 110℃for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 8-3 (11.8 g, yield: 82%).
Elemental analysis structure (C 52H55N3): theoretical value C,86.50; h,7.68; n,5.82; experimental value C,86.48; h,7.67; n,5.83.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 721.4; experimental value 721.4 (M +).
Into a 250mL two-necked flask, 8-3 (14.4 g,20.0 mmol), 8-4 (5.3 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL anhydrous toluene were charged under an argon atmosphere, and the reaction was stirred at 110℃for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 8-5 (15.9 g, yield: 88%).
Elemental analysis structure (C 64H63N3 S): theoretical value C,84.82; h,7.01; n,4.64; experimental value C,84.81; h,7.00; n,4.65.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 905.5; experimental value 906.5 ([ M+H ] +).
Into a 100mL two-necked flask, 8-5 (4.5 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product C-1-3 (3.0 g, yield: 66%).
Elemental analysis structure (C 64H54B3N3 S): theoretical C,82.69; h,5.86; n,4.52; experimental value C,82.71; h,5.85; n,4.51.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 929.4; experimental value 929.4 (M +).
The photophysical properties of the fused ring compound prepared in example 8 of the present invention were examined, and the results are shown in Table 1.
Example 9
The reaction formula is as follows:
9-1 (7.6 g,20.0 mmol), 9-2 (10.7 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give a product 9-3 (10.6 g, yield: 85%).
Elemental analysis structure (C 45H41N3): theoretical value C,86.64; h,6.62; n,6.74; experimental value C,86.67; h,6.62; n,6.75.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 623.3; experimental value 624.3 ([ M+H ] +).
9-3 (12.5 G,20.0 mmol), 9-4 (6.2 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give a product 9-5 (13.0 g, yield: 76%).
Elemental analysis structure (C 57H49N3 Se): theoretical value C,80.07; h,5.78; n,4.91; experimental value C,80.10; h,5.78; n,4.90.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 855.3; experimental value 855.3 (M +).
9-5 (4.3 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give a product D-1-2 (2.0 g, yield: 46%).
Elemental analysis structure (C 64H54B3N3 Se): theoretical C,82.69; h,5.86; n,4.52; experimental value C,82.71; h,5.85; n,4.50.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 879.3; experimental value 879.3 (M +).
The photophysical properties of the fused ring compound prepared in example 9 of the present invention were examined, and the results are shown in Table 1.
Example 10
The reaction formula is as follows:
6-3 (10.0 g,40.0 mmol), 9-2 (7.1 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give a product 10-1 (12.9 g, yield: 95%).
Elemental analysis structure (C 48H40N2O2): theoretical value C,85.18; h,5.96; n,4.14; experimental value C,85.19; h,5.90; n,4.11.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 676.3; experimental value 677.3 ([ M+H ] +).
10-1 (3.4 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give F-1-2 (2.0 g, yield: 57%).
Elemental analysis structure (C 48H31B3N2O2): theoretical value C,82.34; h,4.46; n,4.00; experimental value C,82.35; h,4.47; n,4.00.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 700.3; experimental value 700.3 (M +).
The photophysical properties of the fused ring compound prepared in example 10 of the present invention were examined, and the results are shown in Table 1.
Example 11
The reaction formula is as follows:
11-1 (7.9 g,40.0 mmol), 11-2 (2.5 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (373.6 mg,0.6 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 30mL of anhydrous toluene were put into a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 100℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 11-3 (6.1 g, yield: 90%).
Elemental analysis structure (C 22H16N2O2): theoretical value C,77.63; h,4.74; n,8.23; experimental value C,77.65; h,4.73; n,8.20.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 340.1; experimental value 341.1 ([ M+H ] +).
6-3 (10.0 G,40.0 mmol), 11-3 (6.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 11-4 (12.2 g, yield: 90%).
Elemental analysis structure (C 46H32N2O4): theoretical value C,81.64; h,4.77; n,4.14; experimental value C,81.66; h,4.78; n,4.15.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 676.2; experimental value 676.2 (M +).
11-4 (3.4 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give F-7-1 (1.7 g, yield: 48%).
Elemental analysis structure (C 46H23B3N2O4): theoretical value C,78.91; h,3.31; n,4.00; experimental value C,78.93; h,3.30; n,4.00.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 700.2; experimental value 700.2 (M +).
The photophysical properties of the fused ring compound prepared in example 11 of the present invention were examined, and the results are shown in Table 1.
Example 12
The reaction formula is as follows:
12-1 (17.8 g,60.0 mmol), 12-2 (7.7 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 100mL anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 12-3 (12.0 g, yield: 85%).
Elemental analysis structure (C 44H35BrN2O2): theoretical value C,75.10; h,5.01; n,3.98; experimental value C,75.13; h,5.01; n,3.99.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 702.2; experimental value 703.2 ([ M+H ] +).
Into a 250mL two-necked flask, 12-3 (14.1 g,20.0 mmol), 5-4 (4.5 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butyltetrafluoroborate (348.2 mg,1.2 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and 100mL anhydrous toluene were charged under an argon atmosphere, and the mixture was heated to 110℃and reacted under stirring for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 12-4 (15.6 g, yield: 92%).
Elemental analysis structure (C 60H53N3O2): theoretical value C,84.97; h,6.30; n,4.95; experimental value C,84.98; h,6.29; n,4.96.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 847.4; experimental value 847.4 (M +).
Into a 100mL two-necked flask, 12-4 (4.2 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 20mL of ortho-chlorobenzene were charged under argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The temperature was lowered to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out of the filtration system and washed with toluene to give F-17-5 (1.2 g, yield: 70%).
Elemental analysis structure (C 60H44B3N3O2): theoretical value C,82.70; h,5.09; n,4.82; experimental value C,82.69; h,5.09; n,4.81.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 871.4; experimental value 871.4 (M +).
The photophysical properties of the fused ring compound prepared in example 12 of the present invention were examined, and the results are shown in Table 1.
Example 13
The reaction formula is as follows:
13-1 (11.4 g,40.0 mmol), 5-2 (6.0 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 13-2 (12.9 g, yield: 91%).
Elemental analysis structure (C 45H36Cl2N2O2): theoretical value C,76.37; h,5.13; n,3.96; experimental value C,76.33; h,5.14; n,3.92.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 706.2; experimental value 707.2 ([ M+H ] +).
13-2 (14.2 G,20.0 mmol), 3, 6-di-tert-butylcarbazole (11.2 g,40.0 mmol), NECO-296 (1.5 g,2.4 mmol), sodium tert-butoxide (11.5 g,120.0 mmol) and 150mL of anhydrous mesitylene were put into a 500mL two-necked flask under argon atmosphere, and the mixture was stirred at 130℃for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 13-3 (17.7 g, yield: 74%).
Elemental analysis structure (C 85H84N4O2): theoretical value C,85.53; h,7.09; n,4.69 experimental value C85.55; h,7.06; n,4.64.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1192.7; experimental value 1192.7 (M +).
13-3 (6.0 G,5.0 mmol), boron triiodide (11.8 g,30.0 mmol) and 20mL of 1,2, 4-trichlorobenzene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 90℃and stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product F-17-10 (2.9 g, yield: 47%).
Elemental analysis structure (C 85H75B3N4O2): theoretical value C,83.89; h,6.21; n,4.60; experimental value C,83.90; h,6.21; n,4.57.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1216.6; experimental value 1217.6 ([ M+H ] +).
The photophysical properties of the fused ring compound prepared in example 13 of the present invention were examined, and the results are shown in Table 1.
Example 14
The reaction formula is as follows:
14-1 (6.1 g,20.0 mmol), 14-2 (12.9 g,30.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 14-3 (11.0 g, yield: 84%).
Elemental analysis structure (C 46H56N2 O): theoretical value C,84.61; h,8.64; n,4.29; experimental value C,84.63; h,8.62; n,4.28.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 652.4; experimental value 652.4 (M +).
14-3 (13.1 G,20.0 mmol), 14-4 (6.4 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 80mL of anhydrous toluene were placed in a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 14-5 (15.5 g, yield: 87%).
Elemental analysis structure (C 62H72N2 OS): theoretical value C,83.36; h,8.12; n,3.14; experimental value C,83.37; h,8.11; n,3.14.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 892.5; experimental value 892.5 (M +).
Into a 100mL two-necked flask, 14-5 (4.5 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5G, 5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product G-5-1 (2.3G, yield: 50%).
Elemental analysis structure (C 62H63B3N2 OS): theoretical value C,81.24; h,6.93; n,3.06; experimental value C,81.27; h,6.94; n,3.05.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 916.5; experimental 916.5 (M +).
The photophysical properties of the fused ring compound prepared in example 14 of the present invention were examined, and the results are shown in Table 1.
Example 15
The reaction formula is as follows:
15-1 (10.6 g,40.0 mmol), 15-2 (6.1 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butyl phosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium tert-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 15-3 (11.8 g, yield: 90%).
Elemental analysis structure (C 42H28N2O2S2): theoretical value C,76.80; h,4.30; n,4.27; experimental value C,76.79; h,4.30; n,4.25.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 656.2; experimental value 657.2 ([ M+H ] +).
15-3 (3.3 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product H-1-5 (1.7 g, yield: 51%).
Elemental analysis structure (C 42H19B3N2O2S2): theoretical value C,74.17; h,2.82; n,4.12; experimental value C,74.19; h,2.82; n,4.12.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 680.1; experimental value 681.1 ([ M+H ] +).
The photophysical properties of the fused ring compound prepared in example 15 of the present invention were examined, and the results are shown in Table 1.
Example 16
The reaction formula is as follows:
16-1 (12.6 g,40.0 mmol), 1-2 (5.5 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butyl phosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 16-2 (12.1 g, yield: 83%).
Elemental analysis structure (C 50H36N2S2): theoretical value C,82.38; h,4.98; n,3.84; experimental value C,82.40; h,4.97; n,3.84.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 728.2; experimental value 729.2 ([ M+H ] +).
16-2 (3.6 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give H-3-1 (1.6 g, yield: 43%).
Elemental analysis structure (C 50H27B3N2S2): theoretical value C,79.83; h,3.62; n,3.72; experimental value C,79.86; h,3.61; n,3.70.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 752.2; experimental value 752.2 (M +).
The photophysical properties of the fused ring compound prepared in example 16 of the present invention were examined, and the results are shown in Table 1.
Example 17
The reaction formula is as follows:
17-1 (18.7 g,60.0 mmol), 17-2 (8.4 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were placed in a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 17-3 (13.4 g, yield: 85%).
Elemental analysis structure (C 42H30Br2N2S2): theoretical value C,64.13; h,3.84; n,3.56; experimental value C,64.11; h,3.85; n,3.54.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 784.0; experimental value 784.0 (M +).
17-3 (15.7 G,20.0 mmol), 9, 10-dihydro-9, 9-dimethylacridine (8.4 g,40.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tris (t-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 17-4 (19.8 g, yield: 95%).
Elemental analysis structure (C 72H58N4S2): theoretical value C,82.88; h,5.60; n,5.37; experimental value C,82.90; h,5.57; n,5.36; .
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1042.4; experimental value 1042.4 (M +).
17-4 (5.2 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 30mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product H-17-7 (2.1 g, yield: 40%).
Elemental analysis structure (C 72H49B3N4S2): theoretical value C,81.07; h,4.63; n,5.25; experimental value C,81.09; h,4.61; n,5.22.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1066.4; experimental value 1066.4 (M +).
The photophysical properties of the fused ring compound prepared in example 17 of the present invention were examined, and the results are shown in Table 1.
Example 18
The reaction formula is as follows:
18-1 (12.0 g,40.0 mmol), 5-2 (6.0 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 18-2 (13.5 g, yield: 91%).
Elemental analysis structure (C 45H36Cl2N2S2): theoretical value C,73.06; h,4.90; n,3.79; experimental value C,73.08; h,4.89; n,3.80.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 738.2; experimental value 739.2 ([ M+H ] +).
18-2 (14.8 G,20.0 mmol), 1,3,6, 8-tetramethyl-9H-carbazole (8.9 g,40.0 mmol), NECO-296 (1.5 g,2.4 mmol), sodium t-butoxide (11.5 g,120.0 mmol) and 150mL of anhydrous mesitylene were put into a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 130℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 18-3 (13.4 g, yield: 60%).
Elemental analysis structure (C 77H68N4S2): theoretical value C,83.05; h,6.16; n,5.03; experimental value C,83.06; h,6.16; n,5.02.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1112.5; experimental value 1112.5 (M +).
18-3 (5.6 G,5.0 mmol), boron triiodide (11.8 g,30.0 mmol) and 20mL of 1,2, 4-trichlorobenzene were placed in a 100mL two-necked flask under argon atmosphere, and the mixture was heated to 90℃and stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product H-17-8 (2.5 g, yield: 44%).
Elemental analysis structure (C 77H59B3N4S2): theoretical value C,81.35; h,5.23; n,4.93 experimental value C81.37; h,5.22; n,4.91.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1136.5; experimental value 1136.5 (M +).
The photophysical properties of the fused ring compound prepared in example 18 of the present invention were examined, and the results are shown in Table 1.
Example 19
The reaction formula is as follows:
9-4 (12.5 g,40.0 mmol), 19-1 (8.6 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 80mL of anhydrous toluene were added to a 250mL two-neck flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 19-2 (13.5 g, yield: 77%).
Elemental analysis structure (C 50H40N2Se2): theoretical value C,74.14; h,4.61; n,3.20; experimental value C,74.17; h,4.59; n,3.18.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 876.2; experimental value 876.2 (M +).
19-2 (4.4 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product I-2-2 (1.8 g, yield: 40%).
Elemental analysis structure (C 54H31B3N2Se2): theoretical value C,72.21; h,3.48; n,3.12; experimental value C,72.20; h,3.50; n,3.11.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 900.1; experimental value 900.1 (M +).
The photophysical properties of the fused ring compound prepared in example 19 of the present invention were examined, and the results are shown in Table 1.
Example 20
The reaction formula is as follows:
20-1 (24.9 g,60.0 mmol), 12-2 (6.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 20-2 (14.6 g, yield: 80%).
Elemental analysis structure (C 50H47BrN2Se2): theoretical value C,65.72; h,5.18; n,3.07; experimental value C,65.66; h,5.20; n,3.09.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 914.1; experimental value 914.1 (M +).
20-2 (18.3 G,20.0 mmol) and dry tetrahydrofuran (120 mL) were added dropwise to a 500mL two-necked flask under argon atmosphere, n-butyllithium solution (15.0 mL,1.6M,24.0 mmol) was added dropwise at-78℃and after stirring reaction was completed for 30 minutes, 20-3 (4.5 g,24.0 mmol) was added dropwise, and the reaction solution was returned to room temperature and stirred for 18 hours. The reaction solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution three times, and the organic phase was collected and dried over MgSO 4, and the crude product was separated by column to give product 20-4 (16.1 g, yield: 84%).
Elemental analysis structure (C 56H59BN2O2Se2): theoretical value C,70.00; h,6.19; n,2.92; test value C,69.90; h,6.21; n,2.94.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 962.3; experimental value 962.3 (m+).
20-4 (19.2 G,20.0 mmol), 20-5 (10.4 g,20.0 mmol), tetrakis (triphenylphosphine) palladium (693.4 mg,0.6 mmol), potassium carbonate (8.3 g,60.0 mmol), 120mL tetrahydrofuran and 60mL deionized water were placed in a 500mL two-necked flask under an argon atmosphere, and the mixture was heated to 65℃and stirred for 10 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 20-6 (21.1 g, yield: 85%).
Elemental analysis structure (C 80H66N4Se2): theoretical value C,77.40; h,5.36; n,4.51; experimental value C,77.38; h,5.35; n,4.54.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1242.4; experimental value 1243.4 ([ M+H ] +).
Into a 100mL two-necked flask, 20-6 (6.2 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product I-2-8 (1.5 g, yield: 23%).
Elemental analysis structure (C 80H57B3N4Se2): theoretical value C,75.97; h,4.54; n,4.43; experimental value C,76.00; h,4.51; n,4.45.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1266.3; experimental value 1266.3 (M +).
The photophysical properties of the fused ring compound prepared in example 20 of the present invention were examined, and the results are shown in Table 1.
Example 21
The reaction formula is as follows:
21-1 (8.3 g,40.0 mmol), m-diiodobenzene (15.8 g,48.0 mmol), potassium carbonate (11.1 g,80.0 mmol) and 70mLNMP were placed in a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 130℃and stirred for 14 hours. After the reaction was cooled to room temperature, the reaction solution was settled in 500mL of aqueous sodium chloride solution, the precipitated precipitate was collected, dried under reduced pressure at 70℃to obtain a crude product 21-2 (9.0 g, yield: 55%) by silica gel column separation.
Elemental analysis structure (C 16H11 ISe): theoretical value C,46.97; h,2.71; experimental value C,47.08; h,2.69.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 409.9; experimental value 409.9 (M +).
21-2 (24.5 G,60.0 mmol), 4-2 (6.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 21-3 (13.9 g, yield: 77%).
Elemental analysis structure (C 50H35BrN2Se2): theoretical value C,66.60; h,3.91; n,3.11; experimental value C,66.57; h,3.89; n,3.10.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 902.0; experimental value 902.0 (M +).
21-3 (18.0 G,20.0 mmol), 21-4 (8.6 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butyltetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 120mL of anhydrous toluene were placed in a 500mL two-necked flask under an argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 21-5 (15.0 g, yield: 60%).
Elemental analysis structure (C 82H67N3Se2): theoretical value C,78.64; h,5.39; n,3.36; experimental value C,78.60; h,5.41; n,3.33.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1253.4; experimental value 1254.4 ([ M+H ] +).
21-5 (6.3 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The temperature was lowered to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product I-2-10 (1.3 g, yield: 20%).
Elemental analysis structure (C 82H58B3N3Se2): theoretical value C,77.20; h,4.58; n,3.29; experimental value C,77.25; h,4.57; n,3.30.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1266.3; experimental value 1266.3 (M +).
The photophysical properties of the fused ring compound prepared in example 21 of the present invention were examined, and the results are shown in Table 1.
Example 22
The reaction formula is as follows:
To a 100mL two-necked flask, 11-1 (7.9 g,40.0 mmol), 22-1 (2.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (373.6 mg,0.6 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 30mL anhydrous toluene were charged under an argon atmosphere, and the reaction was stirred at 100℃for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 22-2 (5.9 g, yield: 83%).
Elemental analysis structure (C 23H18N2O2): theoretical value C,77.95; h,5.12; n,7.90; experimental value C,77.89; h,5.11; n,7.88.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 354.1; experimental value 355.1 ([ M+H ] +).
22-3 (26.3 G,60.0 mmol), 22-2 (7.1 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 22-4 (13.6 g, yield: 70%).
Elemental analysis structure (C 47H32Br2N2O2Se2): theoretical value C,57.93; h,3.31; n,2.87; experimental value C,57.89; h,3.29; n,2.90.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 973.9; experimental value 973.9 (M +).
22-4 (9.8 G,10.0 mmol) and dry tetrahydrofuran (110 mL) were added dropwise to a 500mL two-necked flask under argon atmosphere, an n-butyllithium solution (15.0 mL,1.6M,24.0 mmol) was added dropwise at-78℃and after stirring was completed for 30 minutes, 20-3 (4.5 g,24.0 mmol) was added dropwise, and the reaction mixture was returned to room temperature and stirred for 18 hours. The reaction solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution three times, and the organic phase was collected and dried over MgSO 4, and the crude product was separated by column to give product 22-5 (9.3 g, yield: 87%).
Elemental analysis structure (C 56H59B2N2O6Se2): theoretical value C,66.31; h,5.28; n,2.62; test value C,66.34; h,5.29; n,2.59.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1070.3; experimental value 1070.3 (m+).
22-5 (21.4 G,20.0 mmol), 22-6 (14.2 g,20.0 mmol), tetrakis (triphenylphosphine) palladium (693.4 mg,0.6 mmol), potassium carbonate (8.3 g,60.0 mmol), 150mL tetrahydrofuran and 75mL deionized water were placed in a 500mL two-necked flask under an argon atmosphere, and the mixture was heated to 65℃and stirred for 10 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 22-7 (24.9 g, yield: 60%).
Elemental analysis structure (C 139H134N6O2Se2): theoretical value C,80.32; h,6.50; n,4.04; experimental value C,80.35; h,6.48; n,4.02.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 2078.9; experimental value 2079.9 ([ M+H ] +).
Into a 100mL two-necked flask, 22-7 (10.4 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product I-2-13 (1.9 g, yield: 18%).
Elemental analysis structure (C 139H125B3N6O2Se2): theoretical C,79.43; h,5.99; n,4.00; experimental value C,79.46; h,6.01; n,3.98.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 2102.9; experimental value 2102.9 (M +).
The photophysical properties of the fused ring compound prepared in example 22 of the present invention were examined, and the results are shown in Table 1.
Example 23
The reaction formula is as follows:
22-3 (26.3 g,60.0 mmol), 9-2 (7.1 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 110mL of anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 23-1 (14.6 g, yield: 76%).
Elemental analysis structure (C 48H38Br2N2Se2): theoretical value C,60.02; h,3.99; n,2.92; experimental value C,59.99; h,4.01; n,2.94.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 960.0; experimental value 961.0 ([ M+H ] +).
23-1 (9.6 G,10.0 mmol), 23-2 (12.2 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butyltetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 90mL of anhydrous toluene were placed in a 250mL two-necked flask under an argon atmosphere, and the mixture was heated to 110℃and stirred for 20 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 23-3 (12.7 g, yield: 63%).
Elemental analysis structure (C 136H114N8Se2): theoretical value C,80.93; h,5.69; n,5.55; experimental value C,80.89; h,5.71; n,5.52.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 2018.8; experimental value 2019.8 ([ M+H ] +).
In a 100mL two-necked flask, 23-3 (10.1 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged under argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product I-2-19 (2.2 g, yield: 22%).
Elemental analysis structure (C 136H105B3N8Se2): theoretical value C,80.00; h,5.18; n,5.49; experimental value C,79.90; h,5.20; n,5.51.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 2042.7; experimental value 2042.7 (M +).
The photophysical properties of the fused ring compound prepared in example 23 of the present invention were examined, and the results are shown in Table 1.
Example 24
The reaction formula is as follows:
24-1 (24.5 g,60.0 mmol), 24-2 (8.4 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 24-3 (12.7 g, yield: 65%).
Elemental analysis structure (C 42H30Br2N2Te2): theoretical value C,51.60; h,3.09; n,2.87; experimental value C,51.62; h,3.07; n,2.89.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 980.0; experimental value 981.0 ([ M+H ] +).
24-3 (19.6 G,20.0 mmol), carbazole (6.7 g,40.0 mmol), tris (dibenzylideneacetone) dipalladium (549.4 mg,0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg,2.4 mmol), sodium tert-butoxide (7.7 g,80.0 mmol) and 120mL of anhydrous toluene were added to a 250mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and reacted under stirring for 4 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 24-4 (17.3 g, yield: 75%).
Elemental analysis structure (C 66H46N4Te2): theoretical value C,68.91; h,4.03; n,4.87; experimental value C,68.93; h,4.01; n,4.89.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1154.2; experimental value 1154.2 (M +).
24-4 (5.8 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 30mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product L-2-4 (1.6 g, yield: 27%).
Elemental analysis structure (C 66H37B3N4Te2): theoretical value C,67.54; h,3.18; n,4.77; experimental value C,67.56; h,3.17; n,4.75.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1178.1; experimental value 1178.1 (M +).
The photophysical properties of the fused ring compound prepared in example 24 of the present invention were examined, and the results are shown in Table 1.
Example 25
The reaction formula is as follows:
Into a 500mL two-necked flask, 25-1 (27.8 g,60.0 mmol), 12-2 (6.8 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 120mL anhydrous toluene were charged under an argon atmosphere, and the reaction was stirred at 110℃for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 25-2 (10.5 g, yield: 52%).
Elemental analysis structure (C 50H47BrN2Te2): theoretical value C,59.40; h,4.69; n,2.77; experimental value C,59.39; h,4.71; n,2.78.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1014.1; experimental value 1015.1 ([ M+H ] +).
25-2 (20.2 G,20.0 mmol) and dry tetrahydrofuran (130 mL) were added dropwise to a 500mL two-necked flask under argon atmosphere, n-butyllithium solution (15.0 mL,1.6M,24.0 mmol) was added dropwise at-78℃and after stirring reaction was completed for 30 minutes, 20-3 (4.5 g,24.0 mmol) was added dropwise, and the reaction solution was returned to room temperature and stirred for 18 hours. The reaction solution was diluted with ethyl acetate, washed three times with saturated aqueous sodium chloride, and the organic phase was collected and dried over MgSO 4, and the crude product was separated by column to give the product 25-3 (14.2 g, yield: 67%).
Elemental analysis structure (C 56H59BN2O2Te2): theoretical value C,63.57; h,5.62; n,2.65; test value C,63.54; h,5.63; n,2.67.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1062.3; experimental value 1062.3 (m+).
Into a 500mL two-necked flask, 25-3 (21.2 g,20.0 mmol), 20-5 (10.4 g,20.0 mmol), tetrakis (triphenylphosphine) palladium (693.4 mg,0.6 mmol), potassium carbonate (8.3 g,60.0 mmol), 150mL tetrahydrofuran and 75mL deionized water were charged under an argon atmosphere, and the mixture was heated to 65℃and stirred for 10 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 25-4 (12.5 g, yield: 55%).
Elemental analysis structure (C 80H66N4Te2): theoretical value C,71.78; h,4.97; n,4.19; experimental value C,71.78; h,4.99; n,4.21.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1342.3; experimental value 1343.3 ([ M+H ] +).
Into a 100mL two-necked flask, 25-4 (5.7 g,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 30mL o-dichlorobenzene were charged under an argon atmosphere, and the temperature was raised to 180℃and the reaction was stirred for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product L-2-8 (1.4 g, yield: 21%).
Elemental analysis structure (C 80H57B3N4Te2): theoretical value C,70.55; h,4.22; n,4.11; experimental value C,70.57; h,4.19; n,4.09.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1366.3; experimental value 1366.3 (M +).
The photophysical properties of the fused ring compound prepared in example 25 of the present invention were examined, and the results are shown in Table 1.
Example 26
The reaction formula is as follows:
26-1 (29.2 g,60.0 mmol), 26-2 (5.2 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (366.3 mg,0.4 mmol), 1' -bis (diphenylphosphino) ferrocene (443.5 mg,0.8 mmol), sodium t-butoxide (7.7 g,80.0 mmol) and 130mL anhydrous toluene were added to a 500mL two-necked flask under argon atmosphere, and the mixture was heated to 110℃and stirred for 14 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give product 26-3 (9.6 g, yield: 49%).
Elemental analysis structure (C 41H29Br2N3Te2): theoretical value C,50.32; h,2.99; n,4.29; experimental value C,50.24; h,3.00; n,4.31.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 980.9; experimental value 981.9 ([ M+H ] +).
26-3 (9.8 G,10.0 mmol), 26-4 (8.6 g,20.0 mmol), tris (dibenzylideneacetone) dipalladium (274.7 mg,0.3 mmol), tri-tert-butyltetrafluoroborate (348.2 mg,1.2 mmol), sodium tert-butoxide (3.8 g,40.0 mmol) and 90mL of anhydrous toluene were placed in a 250mL two-necked flask under an argon atmosphere, and the mixture was heated to 110℃and stirred for 20 hours. After the reaction was cooled to room temperature, ether was added to dilute, and the mixture was washed three times with saturated aqueous ammonium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by a silica gel column to give 26-5 (10.4 g, yield: 62%).
Elemental analysis structure (C 105H93N5Te2): theoretical value C,75.06; h,5.58; n,4.17; experimental value C,75.03; h,5.60; n,4.15.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1683.6; experimental value 1684.6 ([ M+H ] +).
26-5 (8.4 G,5.0 mmol), boron tribromide (7.5 g,2.9mL,30.0 mmol) and 25mL o-dichlorobenzene were charged into a 100mL two-necked flask under an argon atmosphere, heated to 180℃and stirred for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (4.5 g,5.8mL,35.0 mmol) was added dropwise to the reaction system, the reaction was resumed at room temperature for 30 minutes, and the mixture was allowed to stand, and the solid was separated out from the filtration system and washed with toluene to give the product L-2-17 (1.3 g, yield: 15%).
Elemental analysis structure (C 105H84B3N5Te2): theoretical value C,74.03; h,4.97; n,4.11; experimental value C,73.99; h,4.94; n,4.09.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1707.5; experimental value 1707.5 (M +).
The photophysical properties of the fused ring compound prepared in example 26 of the present invention were examined, and the results are shown in Table 1.
TABLE 1 photophysical Properties of fused Ring Compounds prepared according to the examples of the invention
Note that Δe ST in the table is the difference between the singlet energy level and the triplet energy level, a sample to be measured is prepared by dissolving a compound in toluene solution at a concentration of 10 -4 mol/L, and the difference between the initial (onset) values of the fluorescence spectrum and the phosphorescence spectrum is measured, with a test instrument of HORIBA FluoroMax spectrofluorometer (japan); the delayed fluorescence lifetime was measured by doping a compound at a concentration of 1wt% in polystyrene to prepare a sample to be tested using a time resolved fluorescence spectrometer, test instrument Edinburgh fluorescence spectrometer (FLS-980, uk).
As can be seen from Table 1, the fused ring compounds in the examples provided by the present invention all have a small ΔE ST (< 0.2 eV) and exhibit a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 22 to 41. Mu.s.
The boration agent, the organic solvent, the inert gas, the reaction temperature and time, the base, etc. used in the above examples may be other substances within the above-defined ranges or other values within the ranges, and are not exemplified herein. In addition, the preparation of other compounds not given in the present invention can be carried out with reference to the above-described preparation methods.
Device instance
The process for preparing the device by the organic light-emitting layer through the vacuum evaporation process comprises the following steps: TAPC, TCTA, EML (the mass ratio of the luminescent compound to SiMCP is 1:9) TmPyPB and LiF/Al cathodes are sequentially deposited on indium tin oxide loaded on a glass substrate under the vacuum degree of 4X 10 -4 Pa to obtain the organic electroluminescent device, wherein TAPC and TmPyPB are respectively used as a hole transport layer and an electron transport layer, TCTA is an exciton blocking layer, and the structural formula is as follows:
The specific device structure (device structure a) is:
ITO/TAPC(50nm)/TCTA(5nm)/EML(30nm)/TmPyPB(30nm)/LiF(0.8nm)/Al(100nm)。
The organic light-emitting layer adopts the solution processing technology to prepare the device as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated onto indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating the inventive luminescent compound with SiMCP2 at a spin speed of 1500rpm in a mass ratio of 1:9, and annealing at 80 ℃ for 30 minutes, and then sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under a vacuum degree of 4X 10 -4 Pa to obtain the organic electroluminescent device, wherein the TSPO1 and the TmPyPB are respectively used as a hole blocking layer, an electron transport layer and a main material, and the structural formula is as follows:
the specific device structure (device structure B) is:
ITO/PEDOT:PSS(40nm)/EML(30nm)/TSPO1(8nm)/TmPyPB(42nm)/LiF(1nm)/Al(100nm)。
example 27
Taking A-1-1 in the embodiment 1 as an implementation object, A-1-1 and SiMCP are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with A-1-1 provided by the present invention.
Example 28
Taking A-3-1 in the embodiment 2 as an implementation object, A-3-1 and SiMCP are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with A-3-1 provided herein.
Example 29
Taking A-7-2 in the embodiment 3 as an implementation object, A-7-2 and SiMCP are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with A-7-2 provided herein.
Example 30
Taking A-17-4 in example 4 as an implementation object, A-17-4 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with A-17-4 provided herein.
Example 31
Taking A-17-10 in example 5 as an implementation object, A-17-10 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with A-17-10 provided herein.
Example 32
Taking B-6-1 in example 6 as an implementation object, B-6-1 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with B-6-1 provided by the present invention.
Example 33
Taking B-6-3 in example 7 as an implementation object, B-6-3 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with B-6-3 provided by the present invention.
Example 34
Taking C-1-3 in example 8 as an implementation object, C-1-3 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with C-1-3 provided herein.
Example 35
Taking D-1-2 in the embodiment 9 as an implementation object, D-1-2 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with D-1-2 provided herein.
Example 36
Taking F-1-2 in example 10 as an implementation object, F-1-2 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with F-1-2 provided by the present invention.
Example 37
Taking F-7-1 in example 11 as an implementation object, F-7-1 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with F-7-1 provided herein.
Example 38
Taking F-17-5 in example 12 as an implementation object, F-17-5 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with F-17-5 provided herein.
Example 39
Taking F-17-10 in example 13 as an implementation object, F-17-10 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with F-17-10 provided herein.
Example 40
Taking G-5-1 in example 14 as an implementation object, G-5-1 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with G-5-1 provided by the present invention.
Example 41
Taking H-1-5 in example 15 as an implementation object, H-1-5 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with H-1-5 provided by the present invention.
Example 42
Taking H-3-1 in example 16 as an implementation object, H-3-1 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with H-3-1 provided by the present invention.
Example 43
Taking H-17-7 in example 17 as an implementation object, H-17-7 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with H-17-7 provided by the present invention.
Example 44
Taking H-17-8 in example 18 as an implementation object, H-17-8 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with H-17-8 provided by the present invention.
Example 45
Taking I-2-2 in example 19 as an implementation object, I-2-2 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-2-2 provided herein.
Example 46
Taking I-2-8 in example 20 as an implementation object, mixing I-2-8 with SiMCP according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-2-8 provided herein.
Example 47
Taking I-2-10 in example 21 as an implementation object, I-2-10 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-2-10 provided herein.
Example 48
Taking I-2-13 in example 22 as an implementation object, I-2-13 and SiMCP2 are mixed according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-2-13 provided herein.
Example 49
Taking I-2-19 in example 23 as an implementation object, mixing I-2-19 with SiMCP2 according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-2-19 provided herein.
Example 50
Taking L-2-4 in the embodiment 24 as an implementation object, the mass ratio of L-2-4 to SiMCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with L-2-4 provided herein.
Example 51
Taking L-2-8 in example 25 as an implementation object, the mass ratio of L-2-8 to SiMCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with L-2-8 provided herein.
Example 52
Taking L-2-17 in the embodiment 26 as an implementation object, the mass ratio of L-2-17 to SiMCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with L-2-17 provided herein.
TABLE 2 Performance parameters of electroluminescent devices prepared from the compounds of the invention
Note that: the starting voltage in the table is the driving voltage of the device when the brightness is 1cd m -2; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device and the calculation method described in the literature (Jpn.J.appl.Phys.2001, 40, L783); the half-width is the width of the peak at half the peak height of the electroluminescent spectrum at room temperature, i.e. the midpoint of the peak height is taken as a straight line parallel to the bottom of the peak, which straight line intersects the distance between the two points on both sides of the peak.
As can be seen from Table 2, the device prepared from the fused ring compound provided by the invention has very narrow electroluminescent spectrum, the half-peak width is smaller than 40nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wider (70-100 nm) is solved. Meanwhile, the devices prepared by the fused ring compound provided by the invention have higher device efficiency, and the maximum external quantum efficiency reaches 37.3%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (2)
1. A fused ring compound containing three boron atoms, characterized by one selected from the following structures:
2. An organic electroluminescent device comprising an anode, a cathode, and an organic layer between the anode and the cathode; the organic layer includes a light emitting layer; the light-emitting layer comprising the condensed cyclic compound containing three boron atoms according to claim 1.
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| CN111560030A (en) * | 2019-02-13 | 2020-08-21 | 赛诺拉有限公司 | Organic molecules for optoelectronic devices |
| CN112679310A (en) * | 2019-10-18 | 2021-04-20 | 罗门哈斯电子材料韩国有限公司 | Multiple light emitting materials and organic electroluminescent device comprising the same |
| CN114075222A (en) * | 2020-08-10 | 2022-02-22 | 广州华睿光电材料有限公司 | Boron-containing organic compounds and their use in organic electronic devices |
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2022
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560030A (en) * | 2019-02-13 | 2020-08-21 | 赛诺拉有限公司 | Organic molecules for optoelectronic devices |
| CN112679310A (en) * | 2019-10-18 | 2021-04-20 | 罗门哈斯电子材料韩国有限公司 | Multiple light emitting materials and organic electroluminescent device comprising the same |
| CN114075222A (en) * | 2020-08-10 | 2022-02-22 | 广州华睿光电材料有限公司 | Boron-containing organic compounds and their use in organic electronic devices |
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