CN114426558A - 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
- Publication number
- CN114426558A CN114426558A CN202210145745.1A CN202210145745A CN114426558A CN 114426558 A CN114426558 A CN 114426558A CN 202210145745 A CN202210145745 A CN 202210145745A CN 114426558 A CN114426558 A CN 114426558A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ring compound
- fused ring
- theoretical value
- experimental value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 249
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 216
- 239000010410 layer Substances 0.000 claims description 105
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 100
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 56
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 48
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 29
- -1 heteroaryl ether Chemical compound 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 24
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 3
- 238000005271 boronizing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- VYKNVAHOUNIVTQ-UHFFFAOYSA-N 1,2,2,3,3-pentamethylpiperidine Chemical compound CN1CCCC(C)(C)C1(C)C VYKNVAHOUNIVTQ-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011669 selenium Substances 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 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 3
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 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
- 239000011159 matrix material Substances 0.000 description 79
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 79
- 238000003795 desorption Methods 0.000 description 78
- 238000000921 elemental analysis Methods 0.000 description 77
- 239000000203 mixture Substances 0.000 description 73
- 239000000243 solution Substances 0.000 description 72
- 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
- 238000010790 dilution Methods 0.000 description 49
- 239000012895 dilution Substances 0.000 description 49
- 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
- 239000000047 product Substances 0.000 description 34
- 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 28
- 239000007787 solid Substances 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 26
- 238000007738 vacuum evaporation Methods 0.000 description 18
- 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
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 11
- 230000000903 blocking effect Effects 0.000 description 10
- 239000000758 substrate Substances 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 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
- 125000004429 atom Chemical group 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 230000003111 delayed effect Effects 0.000 description 4
- 238000001194 electroluminescence spectrum Methods 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000012360 testing method Methods 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
- 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
- 238000013459 approach Methods 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-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
- 238000010224 classification analysis Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-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
- 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
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 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
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 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
- 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
- 229910000510 noble metal Inorganic materials 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000007704 transition Effects 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 fused ring compound containing three boron atoms, a preparation method thereof and an electroluminescent device, belonging to the technical field of organic luminescent materials. The structure of the condensed ring compound is shown as a formula (I). The condensed ring compound is characterized in that three boron atoms and electron-rich atoms (oxygen, nitrogen, sulfur, selenium and tellurium) are embedded in a condensed 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, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the relaxation degree of an excited state structure can be reduced by the rigid framework structure of the condensed ring compound, so that the narrow half-peak width is realized. The condensed ring compound of the invention is used as the luminescent layer of the electroluminescent device, and the luminescent layer can not need a filter or a microcavity structureThe narrow half-peak width of electroluminescence is realized, and high external quantum efficiency of the device can be realized. The preparation method of the invention has mild conditions and high product yield.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a fused ring compound containing three boron atoms, a preparation method thereof and an electroluminescent device.
Background
Organic Light Emitting Devices (OLEDs) are generally composed of a cathode, an anode, and organic layers interposed between the cathode and the anode, that is, the device is composed of a transparent ITO anode, a hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission 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 two electrodes, electrons are injected from a cathode, holes are injected from an anode, the electrons and the holes are combined in a light-emitting layer to form an excited state, and the excited state is radiated to return to the ground state, so that the light-emitting device emits light. Due to the characteristics of rich colors, fast response, capability of preparing flexible devices and the like, the organic electroluminescent material is considered as the next generation of flat panel display and solid lighting material with the greatest development prospect.
However, due to the limitation of the statistical law of spin quantum, the conventional fluorescent material can only utilize 25% of singlet excitons in the electroluminescent process, 75% of triplet excitons are lost in the form of non-radiative transition, and the theoretical limit value of the quantum efficiency (IQE) in the device is 25%. Therefore, the full utilization of triplet excitons is one of the effective ways to improve quantum efficiency. For example, phosphorescent metal complexes can convert triplet excitons into photons using spin-orbit coupling of heavy metal atoms, achieving 100% internal quantum efficiency. However, this approach suffers from the problem that phosphorescent metal complexes are expensive. Another approach to utilize triplet excitons is to develop TADF-based light emitting materials that can convert triplet excitons into singlet states using thermally activated delayed fluorescence (RISC) process and emit fluorescence by radiative decay to the ground state, thereby achieving full utilization of singlet and triplet excitons without the need for noble metals.
The main approach for designing TADF materials at present is to achieve a small singlet-triplet energy level difference (Δ E) by introducing donor (D) and acceptor (a) groups such that the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) can be effectively separated spatiallyST) Thereby facilitating the inter-system cross-over process. However, the excited state of the D-A structure shows strong vibrational relaxation, so that the emission spectrum is wide, and the full width at half maximum (FWHM) is generally 70-100nm, resulting in poor color purity. In practical application, it is often necessary to use filters or to construct optical micro-cavities to improve the color purity, but this results in a decrease in the external quantum efficiency of the device or a complicated device structure.
Therefore, how to develop a TADF fluorescent material with narrow spectral characteristics by solving the above-mentioned drawback of wide half-peak width through a suitable chemical structure design 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 fused ring compound containing three boron atoms, a preparation method thereof and an electroluminescent device. The condensed 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 condensed 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, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the relaxation degree of an excited state structure can be reduced by the rigid framework structure of the condensed ring compound, so that the narrow half-peak width is realized. The condensed ring compound of the invention is used as the luminescent layer of the electroluminescent device, and can realize narrow width without optical filter and microcavity structureThe half-peak width of the electroluminescence is wide, and 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 ring compound containing three boron atoms, which has a structure shown in a formula (I):
wherein, X1And X2Each independently selected from N (R)1) O, S, Se or Te;
R1～R7each independently selected from H, D, F, Cl, Br, I, -CN, -CF3Straight chain alkyl of C1-C30, branched chain alkyl of C3-C30, cycloalkyl of C3-C30, alkoxy of C1-C30, alkylthio of C1-C30, aryl of C6-C60, aryl ether of C6-C60, heteroaryl of C3-C60 or heteroaryl ether of C3-C60; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
n1～n7independently selected from integers of 0 to 4;
R1selected from a straight chain alkyl group of H, D, C1-C30, a branched chain alkyl group of C3-C30, a naphthenic group of C3-C30, an aryl group of C6-C60 or a heteroaryl group of C3-C60; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se.
In the above technical solution, it is preferable that: the above-mentioned
And
may also be linked to each other by a single bond, -C (R)1R2)-、-(C＝O)-、-Si(R1R2)-、-N(R1)-、-B(R1)-、-PO(R1) -, -O-, -S-, -Se-, - (S ═ O) -and- (SO)2) -any of the connections is made;
wherein R is1And R2Each independently selected from H, D, C1-C30 straight chain alkyl, C3-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C3-C60 heteroaryl; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se.
In the above technical solution, it is preferable that: the above-mentioned
Each independently selected from the following structures:
L1～L10each independently selected from a straight chain alkyl group of C1-C30, a branched chain alkyl group of C3-C30, a halogenated alkyl group of C1-C30, a naphthenic group of C3-C30, an aromatic group of C6-C60 and a heteroaromatic group of C5-C60; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.
In the above technical solution, the most preferable 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 fused ring compound containing three boron atoms, which comprises the following steps:
under a protective atmosphere, mixing a precursor with a structure shown in a formula (X), a boronizing reagent and an organic solvent, and then carrying out a reaction to obtain a fused ring 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 the same as those of the formula (I).
In the above technical solution, it is preferable that: the boronizing agent is one or more of boron trifluoride, boron trichloride, boron triiodide and boron tribromide; the organic solvent is one or more of toluene, xylene, chlorobenzene, o-dichlorobenzene and 1,2, 4-trichlorobenzene.
In the above technical solution, it is preferable that: the protective atmosphere comprises nitrogen and/or an inert gas.
In the above technical solution, it is preferable that: the reaction temperature is 90-180 ℃, and the reaction time is 20-30 hours, and more preferably 24 hours.
In the above technical solution, it is preferable that: in order to improve the reaction yield, a base may be added on the basis of the above reaction conditions, and the base may include one or more of N, N-diisopropylethylamine, triethylamine, 2,6, 6-tetramethylpiperidine, pentamethylpiperidine, 2, 6-dimethylpyridine, and N, N-dimethyl-p-toluidine.
The invention also provides an organic electroluminescent device, which comprises 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 includes a condensed ring compound containing three boron atoms represented by formula (I) of the present invention.
The structure of the organic electroluminescent device is not particularly limited in the present invention, and may be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art may select and adjust the structure according to the application, quality requirements and product requirements, and the structure of the organic electroluminescent device of the present invention preferably includes:
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 layer of the organic layers is preferably an organic electroluminescent layer; the organic electroluminescent layer preferably comprises one or more fused ring compounds containing three boron atoms represented by formula (I) of the present invention;
a cathode disposed on the organic layer.
The substrate of the present invention is not particularly limited in its choice, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the application, quality requirements, and product requirements, and the substrate of the present invention is preferably glass or plastic. The thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm.
According to the invention, the anode is preferably a material susceptible to hole injection, more preferably a conductive metal or conductive metal oxide, and more preferably indium tin oxide.
The organic layers may be 1 or more, and at least one of the organic layers is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more condensed ring compounds containing three boron atoms shown in the formula (I) of the invention. The condensed ring compound containing three boron atoms shown in the formula (I) is preferably used as a luminescent material to directly form an organic electroluminescent layer.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, 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. The organic layer between the organic electroluminescent layer and the cathode preferably further comprises 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 preparation processes of 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 is preferably prepared by a process of vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing and stereolithography.
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 including an organic electroluminescent layer on the anode; forming a cathode on the organic layer;
the organic electroluminescent layer comprises one or more fused ring compounds containing three boron atoms shown in the formula (I) of the invention.
The structure and material of the organic electroluminescent device in the preparation method, and the corresponding preferred principle, and the corresponding material and structure in the organic electroluminescent device, and the corresponding preferred principle may be corresponding, and are not described in detail herein.
The present invention first forms an anode on a substrate, and the present invention does not specifically limit the manner of forming the anode, and may be performed according to a method known to those skilled in the art. The organic electroluminescent layer and the organic layer below and above the light-emitting layer may be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereoprinting, without any particular limitation. After the organic layer is formed, a cathode is prepared on the surface thereof, and the cathode is formed by a method known to those skilled in the art, including but not limited to vacuum deposition.
The invention has the beneficial effects that:
the condensed 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 condensed 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, thereby realizing smaller Delta ESTAnd the TADF effect, and meanwhile, the rigid framework structure of the condensed cyclic compound can reduce the relaxation degree of an excited state structure, so that a narrow 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 narrow electroluminescent half-peak width can be realized without an optical filter or a microcavity structure, and 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 high product yield.
Detailed Description
In order to further illustrate the present invention, the fused ring compound having three boron atoms, the preparation method thereof and the organic electroluminescent device provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The reagents used in the following examples are all commercially available.
Example 1
The reaction formula is as follows:
1-1(13.0g, 40.0mmol), 1-2(5.2g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 1 to 3(14.2g, 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(3.7g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 20mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product A-1-1(2.3g, yield: 60%).
Elemental analysis Structure (C)54H33B3N4): theoretical value C, 84.20; h, 4.32; n, 7.27; experimental value C, 84.19; h, 4.35; and 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 measured, and the results are shown in table 1.
Example 2
The reaction formula is as follows:
m-phenylenediamine (2.2g, 20.0mmol), 2-bromonaphthalene (8.3g, 40.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (560.1mg, 0.9mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 40mL of anhydrous toluene were added to a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 2-1(6.5g, yield: 90%).
Elemental analysis Structure (C)26H20N2): theoretical value C, 86.64; h, 5.59; n, 7.77; experimental value 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 value 360.2. (M)+)。
1-1(13.0g, 40.0mmol), 2-1(7.2g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 2-2(15.2g, yield: 90%).
Elemental analysis Structure (C)62H46N4): theoretical value C, 87.91; h, 5.47; n, 6.61; experimental value C, 87.89; h, 5.48; and N, 6.64.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 846.4; experimental value 846.4. (M)+)。
2-2(4.3g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were added to a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product A-3-1(2.4g, 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; and 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 measured and the results are shown in table 1.
Example 3
The reaction formula is as follows:
in a 100mL two-necked flask, 3-1(5.0g, 20.0mmol), 3-2(7.3g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (275.0mg, 0.3mmol), 1,1' -bis (diphenylphosphino) ferrocene (332.6mg, 0.6mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 40mL of anhydrous toluene were added under an argon atmosphere, and the reaction was stirred at 110 ℃ for 20 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 3-3(6.2g, yield: 85%).
Elemental analysis Structure (C)20H14BrNO): theoretical value C, 65.95; h, 3.87; n, 3.85; experimental value C, 65.94; h, 3.86; and N, 3.87.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 363.0; experimental value 363.0 (M)+)。
In a 250mL two-necked flask, 3-3(14.6g, 40.0mmol), 1-2(7.3g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 3-4(15.2g, yield: 92%).
Elemental analysis Structure (C)58H42N4O2): theoretical value C, 84.24; h, 5.12; n, 6.77; experimental value C, 84.21; h, 5.10; and N, 6.80.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 826.3; experimental value 826.3 (M)+)。
In a 100mL two-necked flask, 3-4(4.1g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 20mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product A-7-2(2.4g, 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; and 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 measured, and the results are shown in table 1.
Example 4
The reaction formula is as follows:
in a 500mL two-necked flask, under an argon atmosphere, 4-1(22.3g, 60.0mmol), 4-2(6.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added, and the reaction was stirred at 110 ℃ for 14 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 4-3(14.4g, 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; and N, 6.76.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical 824.3; experimental value 825.3([ M + H)]+)。
In a 250mL two-necked flask, 4-3(16.5g, 20.0mmol), 3, 6-di-tert-butylcarbazole (5.6g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 100mL of anhydrous toluene were added under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 4-4(18.4g, yield: 90%).
Elemental analysis structure(C74H65N5): theoretical value C, 86.77; h, 6.40; n, 6.84; experimental value C, 86.75; h, 6.39; and N, 6.82.
Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1023.5; experimental value 1023.5 (M)+)。
In a 100mL two-necked flask, 4-4(5.1g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 20mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product A-17-4(3.7g, yield: 68%).
Elemental analysis Structure (C)76H64B3N5): theoretical value C, 84.54; h, 5.97; n,6.49 experimental value C, 84.52; h, 5.96; and 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 measured, and the results are shown in table 1.
Example 5
The reaction formula is as follows:
5-1(14.4g, 40.0mmol), 5-2(6.0g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 5-3(16.0g, yield: 93%).
Element classificationAnalysis structure (C)57H46Cl2N4): theoretical value C, 79.80; h, 5.40; n, 6.53; experimental value C, 79.84; h, 5.39; and N, 6.52.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: a theoretical value of 856.3; experimental value 857.3([ M + H)]+)。
5-3(17.2g, 20.0mmol), 5-4(9.0g, 40.0mmol), NECO-296(1.5g, 2.4mmol), sodium tert-butoxide (11.5g, 120.0mmol) and 150mL of anhydrous mesitylene were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 130 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 5 to 5(17.3g, 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(6.2g, 5.0mmol), boron triiodide (11.8g,30.0mmol) and 20mL of 1,2, 4-trichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 90 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product A-17-10(3.2g, yield: 50%).
Elemental analysis Structure (C)89H73B3N6): theoretical value C, 84.90; h, 5.84; n,6.68 experimental value C, 84.88; h, 5.85; and 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 measured, and the results are shown in table 1.
Example 6
The reaction formula is as follows:
6-1(7.3g, 20.0mmol), 5-2(9.1g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 40mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 6-2(9.4g, 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; and N, 7.13.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: a theoretical value of 587.3; experimental value 588.3([ M + H)]+)。
6-2(11.8g, 20.0mmol), 6-3(5.0g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 6-4(13.9g, yield: 92%).
Elemental analysis Structure (C)55H49N3O) theoretical value C, 85.79; h, 6.53; n, 5.56; experimental value C, 85.77; h, 6.54; and 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(3.8g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 20mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give product B-6-1(2.3g, yield: 60%).
Elemental analysis Structure (C)54H40B3N3O): theoretical value C, 83.22; h, 5.17; n, 5.39; experimental value C, 83.24; h, 5.16; and 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 measured, and the results are shown in table 1.
Example 7
The reaction formula is as follows:
1-1(6.5g, 20.0mmol), 7-1(9.9g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 40mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 7-2(8.6g, yield: 75%).
Elemental analysis Structure (C)36H27Cl2N3): theoretical value C, 75.52; h, 4.75; n, 7.34; experimental value C, 75.50; h, 4.74; and 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(11.5g, 20.0mmol), 6-3(5.0g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed three times with saturated aqueous ammonium chloride solution, 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(13.5g, yield: 91%).
Elemental analysis Structure (C)48H35Cl2N3O): theoretical value C, 77.83; h, 4.76; n, 5.67; experimental value C, 77.80; h, 4.77; and 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 ]]+)。
In a 500mL two-necked flask, 7-3(11.5g, 20.0mmol), 3, 6-di-tert-butylcarbazole (11.2g, 40.0mmol), NECO-296(1.5mg, 2.4mmol), sodium tert-butoxide (11.5g, 120.0mmol) and 150mL of anhydrous mesitylene were added under an argon atmosphere, and the mixture was heated to 130 ℃ and stirred for reaction for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 7-4(18.2g, yield: 74%).
Elemental analysis Structure (C)88H83N5O): theoretical value C, 86.17; h, 6.82; n, 5.71; experimental value C, 86.11; h, 6.81; and N, 5.70.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1225.7; experimental value 1225.7 (M)+)。
In a 100mL two-necked flask, 7-4(6.1g, 5.0mmol), boron triiodide (11.8g,30.0mmol) and 20mL of 1,2, 4-trichlorobenzene were placed under an argon atmosphere, and the reaction was stirred at 90 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product B-6-3(3.4g, yield: 55%).
Elemental analysis Structure (C)88H74B3N5O): theoretical value C, 84.56; h, 5.97; n, 5.60; experimental value C, 84.59; h, 5.96; and 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 measured, and the results are shown in table 1.
Example 8
The reaction formula is as follows:
8-1(9.0g, 20.0mmol), 8-2(12.0g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 8-3(11.8g, 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: a theoretical value of 721.4; experimental value 721.4 (M)+)。
8-3(14.4g, 20.0mmol), 8-4(5.3g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed three times with saturated aqueous ammonium chloride solution, 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 8-5(15.9g, yield: 88%).
Elemental analysis Structure (C)64H63N3S): theoretical value C, 84.82; h, 7.01; n, 4.64; experimental value C, 84.81; h, 7.00; and 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)]+)。
8-5(4.5g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product C-1-3(3.0g, yield: 66%).
Elemental analysis Structure (C)64H54B3N3S): theoretical value 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 measured, and the results are shown in table 1.
Example 9
The reaction formula is as follows:
in a 250mL two-necked flask, 9-1(7.6g, 20.0mmol), 9-2(10.7g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 9-3(10.6g, 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; and 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)]+)。
In a 250mL two-necked flask, 9-3(12.5g, 20.0mmol), 9-4(6.2g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 9-5(13.0g, yield: 76%).
Elemental analysis Structure (C)57H49N3Se): theoretical value C, 80.07; h, 5.78; n, 4.91; experimental value C, 80.10; h, 5.78; and N, 4.90.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 855.3; experimental value 855.3 (M)+)。
In a 100mL two-necked flask, 9-5(4.3g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product D-1-2(2.0g, yield: 46%).
Elemental analysis Structure (C)64H54B3N3Se): theoretical value C, 82.69; h, 5.86; n, 4.52; experimental value C, 82.71; h, 5.85; and 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 measured and the results are shown in table 1.
Example 10
The reaction formula is as follows:
6-3(10.0g, 40.0mmol), 9-2(7.1g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 10-1(12.9g, 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)]+)。
In a 100mL two-necked flask, 10-1(3.4g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give a product F-1-2(2.0g, 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; and N, 4.00.
Matrix assisted laserDesorption 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 measured and the results are shown in table 1.
Example 11
The reaction formula is as follows:
in a 100mL two-necked flask under an argon atmosphere were charged 11-1(7.9g, 40.0mmol), 11-2(2.5g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (373.6mg, 0.6mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 30mL of anhydrous toluene, and the reaction was stirred at 100 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 11-3(6.1g, 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; and N, 8.20.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 340.1; experimental value 341.1([ M + H)]+)。
6-3(10.0g, 40.0mmol), 11-3(6.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 11-4(12.2g, 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; and N, 4.15.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 676.2; experimental value 676.2 (M)+)。
In a 100mL two-necked flask, 11-4(3.4g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product F-7-1(1.7g, 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; and 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 measured and the results are shown in table 1.
Example 12
The reaction formula is as follows:
12-1(17.8g, 60.0mmol), 12-2(7.7g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium t-butoxide (7.7g, 80.0mmol) and 100mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 12-3(12.0g, 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; and N, 3.99.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 702.2; experimental value 703.2([ M + H)]+)。
In a 250mL two-necked flask, 12-3(14.1g, 20.0mmol), 5-4(4.5g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butyltetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 100mL of anhydrous toluene were added under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 12-4(15.6g, 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; and N, 4.96.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: a theoretical value of 847.4; experimental value 847.4 (M)+)。
12-4(4.2g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 20mL of ortho-chlorobenzene were added to a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product F-17-5(1.2g, 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; and 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 measured, and the results are shown in table 1.
Example 13
The reaction formula is as follows:
13-1(11.4g, 40.0mmol), 5-2(6.0g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 13-2(12.9g, 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: a theoretical value of 706.2; experimental value 707.2([ M + H ]]+)。
13-2(14.2g, 20.0mmol), 3, 6-di-tert-butylcarbazole (11.2g, 40.0mmol), NECO-296(1.5g, 2.4mmol), sodium tert-butoxide (11.5g, 120.0mmol) and 150mL of anhydrous mesitylene were added to a 500mL two-necked flask under an argon atmosphere, and the mixture was heated to 130 ℃ and stirred for reaction for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 13-3(17.7g, yield: 74%).
Elemental analysis Structure (C)85H84N4O2): theoretical value C, 85.53; h, 7.09; n,4.69 experimental value C, 85.55; h, 7.06; and 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(6.0g, 5.0mmol), boron triiodide (11.8g,30.0mmol) and 20mL of 1,2, 4-trichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 90 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product F-17-10(2.9g, 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; and 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 measured, and the results are shown in table 1.
Example 14
The reaction formula is as follows:
14-1(6.1g, 20.0mmol), 14-2(12.9g, 30.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 14-3(11.0g, yield: 84%).
Elemental analysis Structure (C)46H56N2O): theoretical value C, 84.61; h, 8.64; n, 4.29; experimental value C, 84.63; h, 8.62; and N, 4.28.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 652.4; experimental values652.4(M+)。
14-3(13.1g, 20.0mmol), 14-4(6.4g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 14-5(15.5g, yield: 87%).
Elemental analysis Structure (C)62H72N2OS): theoretical value C, 83.36; h, 8.12; n, 3.14; experimental value C, 83.37; h, 8.11; and N, 3.14.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 892.5; experimental value 892.5 (M)+)。
14-5(4.5g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5G,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the reaction was allowed to stand, and the solid precipitated in the filtration system and washed with toluene to give product G-5-1(2.3G, yield: 50%).
Elemental analysis Structure (C)62H63B3N2OS): theoretical value C, 81.24; h, 6.93; n, 3.06; experimental value C, 81.27; h, 6.94; and N, 3.05.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 916.5; experimental value 916.5 (M)+)。
The photophysical properties of the fused ring compound prepared in example 14 of the present invention were measured, and the results are shown in table 1.
Example 15
The reaction formula is as follows:
in a 250mL two-necked flask under an argon atmosphere, 15-1(10.6g, 40.0mmol), 15-2(6.1g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added, and the reaction was stirred at 110 ℃ for 14 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 15-3(11.8g, 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; and 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)]+)。
In a 100mL two-necked flask, 15-3(3.3g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product H-1-5(1.7g, 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; and 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 measured, and the results are shown in table 1.
Example 16
The reaction formula is as follows:
16-1(12.6g, 40.0mmol), 1-2(5.5g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed three times with a saturated aqueous ammonium chloride solution, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 16-2(12.1g, 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; and 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(3.6g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give H-3-1(1.6g, 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; and 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 results of examining the photophysical properties of the fused ring compound prepared in example 16 of the present invention are shown in table 1.
Example 17
The reaction formula is as follows:
17-1(18.7g, 60.0mmol), 17-2(8.4g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 17-3(13.4g, 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(15.7g, 20.0mmol), 9, 10-dihydro-9, 9-dimethylacridine (8.4g, 40.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added to a 250mL two-necked flask under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed three times with saturated aqueous ammonium chloride solution, 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 17-4(19.8g, 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(5.2g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 30mL of o-dichlorobenzene were charged in a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the reaction was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product H-17-7(2.1g, 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; and 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 measured, and the results are shown in table 1.
Example 18
The reaction formula is as follows:
18-1(12.0g, 40.0mmol), 5-2(6.0g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 100mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 18-2(13.5g, 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; and 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(14.8g, 20.0mmol), 1,3,6, 8-tetramethyl-9H-carbazole (8.9g, 40.0mmol), NECO-296(1.5g, 2.4mmol), sodium tert-butoxide (11.5g, 120.0mmol) and 150mL of anhydrous mesitylene were added to a 500mL two-neck flask under an argon atmosphere, and the reaction was stirred at 130 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 18-3(13.4g, 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; and 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(5.6g, 5.0mmol), boron triiodide (11.8g,30.0mmol) and 20mL of 1,2, 4-trichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 90 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the reaction was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product H-17-8(2.5g, yield: 44%).
Elemental analysis Structure (C)77H59B3N4S2): theoretical value C, 81.35; h, 5.23; n,4.93 experimental value C, 81.37; h, 5.22; and 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 measured, and the results are shown in table 1.
Example 19
The reaction formula is as follows:
9-4(12.5g, 40.0mmol), 19-1(8.6g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 80mL of anhydrous toluene were added to a 250mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 19-2(13.5g, 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; and 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(4.4g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product I-2-2(1.8g, 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 measured, and the results are shown in table 1.
Example 20
The reaction formula is as follows:
20-1(24.9g, 60.0mmol), 12-2(6.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 20-2(14.6g, 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; and 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(18.3g,20.0mmol) and dry tetrahydrofuran (120mL) were added dropwise to a 500mL two-necked flask under an argon atmosphere, an n-butyllithium solution (15.0mL,1.6M,24.0mmol) was added dropwise at-78 deg.C, and after stirring and reacting for 30 minutes, 20-3(4.5g,24.0mmol) was added dropwise, and the reaction mixture was returned to room temperature and stirred and reacted for 18 hours. The reaction solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution three times, the organic phase was collected and MgSO4The crude product was dried and separated by column to give product 20-4(16.1g, 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; and 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(19.2g, 20.0mmol), 20-5(10.4g, 20.0mmol), tetrakis (triphenylphosphine) palladium (693.4mg, 0.6mmol), potassium carbonate (8.3g, 60.0mmol), 120mL of tetrahydrofuran and 60mL of deionized water were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 65 ℃ for 10 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 20-6(21.1g, 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)]+)。
20-6(6.2g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product I-2-8(1.5g, 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; and 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 measured and the results are shown in table 1.
Example 21
The reaction formula is as follows:
21-1(8.3g, 40.0mmol), m-diiodobenzene (15.8g, 48.0mmol), potassium carbonate (11.1g, 80.0mmol) and 70mL of NMMP were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 130 ℃ for 14 hours. After the reaction was cooled to room temperature, the reaction solution was settled in 500mL of an aqueous solution of sodium chloride, filtered, and the precipitate was collected, dried under reduced pressure at 70 ℃ and the crude product was separated by means of a silica gel column to obtain 21-2(9.0g, yield: 55%).
Elemental analysis Structure (C)16H11ISe): 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(24.5g, 60.0mmol), 4-2(6.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give product 21-3(13.9g, 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; and 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(18.0g, 20.0mmol), 21-4(8.6g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butyltetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 120mL of anhydrous toluene were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 21-5(15.0g, 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(6.3g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL o-dichlorobenzene were charged in a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give product I-2-10(1.3g, 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; and 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 measured, and the results are shown in table 1.
Example 22
The reaction formula is as follows:
in a 100mL two-necked flask, under an argon atmosphere, 11-1(7.9g, 40.0mmol), 22-1(2.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (373.6mg, 0.6mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 30mL of anhydrous toluene were added, and the reaction was stirred at 100 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 22-2(5.9g, 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)]+)。
In a 500mL two-necked flask, under an argon atmosphere, 22-3(26.3g, 60.0mmol), 22-2(7.1g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 22-4(13.6g, 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; and N, 2.90.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 973.9; experimental value 973.9 (M)+)。
Under an argon atmosphere, 22-4(9.8g,10.0mmol) and dry tetrahydrofuran (110mL) were added dropwise to a 500mL two-necked flask, an n-butyllithium solution (15.0mL,1.6M,24.0mmol) was added dropwise at-78 deg.C, and after stirring reaction was completed for 30 minutes, 20-3(4.5g,24.0mmol) was added dropwise, and the reaction mixture was returned to room temperature and stirred for reaction for 18 hours. The reaction solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution three times, the organic phase was collected and MgSO4The crude product was dried and separated by column to give 22-5(9.3g, 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; and N, 2.59.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1070.3; experimental value 1070.3(M +).
In a 500mL two-necked flask, under an argon atmosphere, 22-5(21.4g, 20.0mmol), 22-6(14.2g, 20.0mmol), tetrakis (triphenylphosphine) palladium (693.4mg, 0.6mmol), potassium carbonate (8.3g, 60.0mmol), 150mL of tetrahydrofuran and 75mL of deionized water were added, and the reaction was stirred at 65 ℃ for 10 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 22-7(24.9g, 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; and 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)]+)。
In a 100mL two-necked flask, 22-7(10.4g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give the product I-2-13(1.9g, yield: 18%).
Elemental analysis Structure (C)139H125B3N6O2Se2): theoretical value C, 79.43; h, 5.99; n, 4.00; experimental value C, 79.46; h, 6.01; and 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 measured, and the results are shown in table 1.
Example 23
The reaction formula is as follows:
in a 500mL two-necked flask, under an argon atmosphere, 22-3(26.3g, 60.0mmol), 9-2(7.1g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 110mL of anhydrous toluene were added, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 23-1(14.6g, 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; and N, 2.94.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 960.0; experimental value 961.0([ M + H ]]+)。
23-1(9.6g, 10.0mmol), 23-2(12.2g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butyltetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 90mL of anhydrous toluene were added to a 250mL two-necked flask under an argon atmosphere, and the reaction was stirred at 110 ℃ for 20 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 23-3(12.7g, 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; and 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)]+)。
23-3(10.1g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give product I-2-19(2.2g, 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 measured, and the results are shown in table 1.
Example 24
The reaction formula is as follows:
in a 500mL two-necked flask, 24-1(24.5g, 60.0mmol), 24-2(8.4g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to give 24-3(12.7g, 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; and 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)]+)。
In a 250mL two-necked flask, 24-3(19.6g, 20.0mmol), carbazole (6.7g, 40.0mmol), tris (dibenzylideneacetone) dipalladium (549.4mg, 0.6mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3mg, 2.4mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added under an argon atmosphere, and the reaction was stirred at 110 ℃ for 4 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 24-4(17.3g, 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; and N, 4.89.
Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1154.2; experimental value 1154.2 (M)+)。
In a 100mL two-necked flask, 24-4(5.8g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 30mL of o-dichlorobenzene were charged under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give L-2-4(1.6g, 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; and 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 measured, and the results are shown in table 1.
Example 25
The reaction formula is as follows:
in a 500mL two-necked flask, 25-1(27.8g, 60.0mmol), 12-2(6.8g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 120mL of anhydrous toluene were added 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 for dilution, and the mixture was washed three times with a saturated aqueous ammonium chloride solution, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 25-2(10.5g, 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(20.2g,20.0mmol) and dry tetrahydrofuran (130mL) were added dropwise to a 500mL two-necked flask under an argon atmosphere, an n-butyllithium solution (15.0mL,1.6M,24.0mmol) was added dropwise at-78 ℃, and after stirring and reacting for 30 minutes, 20-3(4.5g,24.0mmol) was added dropwise, and the reaction mixture was returned to room temperature and stirred and reacted for 18 hours. The reaction solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution three times, the organic phase was collected and MgSO4The crude product was dried and separated by column to give 25-3(14.2g, 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: a theoretical value of 1062.3; experimental value 1062.3(M +).
25-3(21.2g, 20.0mmol), 20-5(10.4g, 20.0mmol), tetrakis (triphenylphosphine) palladium (693.4mg, 0.6mmol), potassium carbonate (8.3g, 60.0mmol), 150mL of tetrahydrofuran and 75mL of deionized water were added to a 500mL two-necked flask under an argon atmosphere, and the reaction was stirred at 65 ℃ for 10 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 25-4(12.5g, yield: 55%).
Element classificationAnalysis 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)]+)。
25-4(5.7g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 30mL of o-dichlorobenzene were charged in a 100mL two-neck flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the mixture was allowed to stand, and a solid was precipitated from the filtered system and washed with toluene to give L-2-8(1.4g, 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; and 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 measured, and the results are shown in table 1.
Example 26
The reaction formula is as follows:
26-1(29.2g, 60.0mmol), 26-2(5.2g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (366.3mg, 0.4mmol), 1,1' -bis (diphenylphosphino) ferrocene (443.5mg, 0.8mmol), sodium tert-butoxide (7.7g, 80.0mmol) and 130mL of anhydrous toluene were added to a 500mL two-necked flask 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 for dilution, and the mixture was washed with saturated aqueous ammonium chloride solution three times, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 26-3(9.6g, 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: a theoretical value of 980.9; experimental value 981.9([ M + H)]+)。
26-3(9.8g, 10.0mmol), 26-4(8.6g, 20.0mmol), tris (dibenzylideneacetone) dipalladium (274.7mg, 0.3mmol), tri-tert-butyltetrafluoroborate (348.2mg, 1.2mmol), sodium tert-butoxide (3.8g, 40.0mmol) and 90mL of anhydrous toluene were added to a 250mL two-necked flask under an argon atmosphere, and the reaction was stirred at a temperature of 110 ℃ for 20 hours. After the reaction was cooled to room temperature, ether was added for dilution, and the mixture was washed three times with a saturated aqueous ammonium chloride solution, and the organic phase was collected, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the crude product was separated by means of a silica gel column to obtain 26-5(10.4g, 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; and 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(8.4g, 5.0mmol), boron tribromide (7.5g,2.9mL,30.0mmol) and 25mL of o-dichlorobenzene were charged in a 100mL two-necked flask under an argon atmosphere, and the reaction was stirred at 180 ℃ for 24 hours. The reaction was cooled to 0 ℃ and N, N-diisopropylethylamine (4.5g,5.8mL,35.0mmol) was added dropwise to the reaction system, the reaction was allowed to return to room temperature for 30 minutes, the reaction was allowed to stand, and the solid precipitated in the filtration system and washed with toluene to give L-2-17(1.3g, 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; and 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 results of examining the photophysical properties of the fused ring compound prepared in example 26 of the present invention are shown in table 1.
TABLE 1 photophysical properties of fused ring compounds prepared in the examples of the present invention
Note,. DELTA.E in the TableSTIs the difference between the singlet level and the triplet level, obtained by reacting the compound with 10-4A test sample was prepared by dissolving the concentration of mol/L in a toluene solution, and the difference between the initial (onset) value of the fluorescence spectrum and the phosphorescence spectrum was measured with a HORIBA FluoroMax spectrophotometer (Japan); the delayed fluorescence lifetime was measured by doping a sample of polystyrene with a compound at a concentration of 1 wt% and measuring the sample by means of a time-resolved fluorescence spectrometer, the measuring instrument being an Edinburgh fluorescence spectrometer (FLS-980, UK).
As can be seen from Table 1, the condensed ring compounds in the examples provided by the present invention all have smaller Δ EST(<0.2eV), and exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 22 to 41 μ s.
The boronating agent, the organic solvent, the inert gas, the reaction temperature and time, the base, etc. used in the above examples may also be other substances within the above-defined ranges, or other values within the ranges, which are not exemplified herein. In addition, other compounds not given in the present invention can be prepared by referring to the above-mentioned preparation method.
Device examples
The process of preparing the device by the organic light-emitting layer by adopting a vacuum evaporation process is as follows: on indium tin oxide supported on a glass substrate, 4X 10-4Sequentially depositing TAPC, TCTA, EML (the luminescent compound is mixed with SiMCP2 according to the mass ratio of 1: 9), TmPyPB and LiF/Al cathode under the vacuum degree of Pa,obtaining 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 shown 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 process of preparing the device by adopting the solution processing technology for the organic light-emitting layer is as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and then spin-coated with the inventive light-emitting compound and SiMCP2 at a mass ratio of 1: 9 the mixed toluene solution was annealed at 80 ℃ for 30 minutes for 1 minute, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and LiF/Al cathodes under Pa vacuum degree to obtain the organic electroluminescent device, wherein TSPO1 and TmPyPB are respectively used as a hole blocking layer, an electron transport layer and a main body material, and the structural formulas are 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
A-1-1 in example 1 was used as an object, and the ratio of A-1-1 to SiMCP2 was adjusted in the 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with A-1-1 provided by the present invention.
Example 28
A-3-1 in example 2 was used as an implementation object, and the mass ratio of A-3-1 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with A-3-1 provided by the present invention.
Example 29
A-7-2 in example 3 was used as an implementation object, and the mass ratio of A-7-2 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with A-7-2 provided by the present invention.
Example 30
A-17-4 in example 4 was used as an implementation target, and the mass ratio of A-17-4 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with A-17-4 provided by the present invention.
Example 31
Taking A-17-10 in example 5 as an implementation object, mixing A-17-10 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with A-17-10 provided by the present invention.
Example 32
B-6-1 in example 6 was used as an implementation target, and the mass ratio of B-6-1 to SiMCP2 was 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with B-6-1 provided by the present invention.
Example 33
B-6-3 in example 7 was used as an object, and the mass ratio of B-6-3 to SiMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with B-6-3 provided by the present invention.
Example 34
C-1-3 in example 8 was used as an implementation target, and the mass ratio of C-1-3 to SiMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, the organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with C-1-3 provided by the present invention.
Example 35
D-1-2 in example 9 was used as an object of implementation, and the mass ratio of D-1-2 to SiMCP2 was 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with D-1-2 provided by the present invention.
Example 36
F-1-2 in example 10 was used as an object, and the mass ratio of F-1-2 to SiMCP2 was 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with F-1-2 provided by the present invention.
Example 37
F-7-1 in example 11 was used as a target, and the mass ratio of F-7-1 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with F-7-1 provided by the present invention.
Example 38
F-17-5 in example 12 was used as an implementation target, and the mass ratio of F-17-5 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with F-17-5 provided by the present invention.
Example 39
F-17-10 in example 13 was used as a target, and the mass ratio of F-17-10 to SiMCP2 was 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with F-17-10 provided by the present invention.
Example 40
With G-5-1 in example 14 as an implementation target, the mass ratio of G-5-1 to SiMCP2 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with G-5-1 provided by the present invention.
EXAMPLE 41
H-1-5 in example 15 was used as an implementation object, and H-1-5 and SiMCP2 were mixed according to the 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with H-1-5 provided by the present invention.
Example 42
H-3-1 in example 16 was used as an implementation target, and the mass ratio of H-3-1 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with H-3-1 provided by the present invention.
Example 43
H-17-7 in example 17 was used as an implementation target, and the mass ratio of H-17-7 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with H-17-7 provided by the present invention.
Example 44
H-17-8 in example 18 was used as an implementation target, and the mass ratio of H-17-8 to SiMCP2 was 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of 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, mixing the I-2-2 and SiMCP2 according to the 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with I-2-2 provided by the present invention.
Example 46
Taking I-2-8 in example 20 as an implementation object, mixing I-2-8 and SiMCP2 according to the 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with I-2-8 provided by the present invention.
Example 47
Taking I-2-10 in example 21 as an implementation object, mixing I-2-10 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with I-2-10 provided by the present invention.
Example 48
Taking I-2-13 in example 22 as an implementation object, mixing I-2-13 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with I-2-13 provided by the present invention.
Example 49
Taking I-2-19 in example 23 as an implementation object, mixing the I-2-19 and SiMCP2 according to the 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 utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with I-2-19 provided by the present invention.
Example 50
Taking L-2-4 in example 24 as an implementation object, mixing the L-2-4 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with L-2-4 provided by the present invention.
Example 51
Taking L-2-8 in example 25 as an implementation object, mixing the L-2-8 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with L-2-8 provided by the present invention.
Example 52
Taking L-2-17 in example 26 as an implementation object, mixing L-2-17 and SiMCP2 according to the 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 utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with L-2-17 provided by the present invention.
Table 2 performance parameters of electroluminescent devices prepared from the compounds provided by the invention
Note: the on-voltage in the table is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device by the calculation method described in the literature (Jpn.J.appl.Phys.2001,40, L783); the half-peak width is the peak width at half of the spectral peak height of the electroluminescence spectrum at room temperature, i.e. a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the straight line is the distance between two intersecting 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 a very narrow electroluminescence spectrum, the half-peak width of the device is less than 40nm, and the problem that the traditional TADF compound with a D-A structure has a wide electroluminescence spectrum (70-100 nm) is solved. Meanwhile, 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 should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A fused ring compound containing three boron atoms, characterized by having a structure represented by formula (I):
wherein, X1And X2Each independently selected from N (R)1) O, S, Se or Te;
R1～R7each independently selected from H, D, F, Cl, Br, I, -CN, -CF3Straight chain alkyl of C1-C30, branched chain alkyl of C3-C30, cycloalkyl of C3-C30, alkoxy of C1-C30, alkylthio of C1-C30, aryl of C6-C60, aryl ether of C6-C60, heteroaryl of C3-C60 or heteroaryl ether of C3-C60; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
n1～n7independently selected from integers of 0 to 4;
R1selected from a straight chain alkyl group of H, D, C1-C30, a branched chain alkyl group of C3-C30, a naphthenic group of C3-C30, an aryl group of C6-C60 or a heteroaryl group of C3-C60; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se.
2. A fused ring compound containing three boron atoms as claimed in claim 1, wherein said fused ring compound contains three boron atoms
And
may also be linked to each other by a single bond, -C (R)1R2)-、-(C＝O)-、-Si(R1R2)-、-N(R1)-、-B(R1)-、-PO(R1)-、-O-、-S-、-Se-、-(S＝O)-、-(SO2) -any of the connections is made;
wherein R is1And R2Each independently selected from H, D, C1-C30 straight chain alkyl, C3-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C3-C60 heteroaryl; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se.
3. A fused ring compound containing three boron atoms as claimed in claim 1, wherein said fused ring compound contains three boron atoms
Each independently selected from the following structures:
L1～L10each independently selected from a straight chain alkyl group of C1-C30, a branched chain alkyl group of C3-C30, a halogenated alkyl group of C1-C30, a naphthenic group of C3-C30, an aromatic group of C6-C60 and a heteroaromatic group of C5-C60; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.
4. A fused ring compound containing three boron atoms as claimed in claim 1, selected from one of the following structures:
5. a process for the preparation of fused ring compounds containing three boron atoms as claimed in any one of claims 1 to 4, comprising the steps of:
under a protective atmosphere, mixing a precursor with a structure shown in a formula (X), a boronizing reagent and an organic solvent, and then carrying out a reaction to obtain a fused ring compound containing three boron atoms shown in a formula (I);
the definitions of the substituent groups and the number thereof in the above structural formula are defined in claims 1 to 4.
6. A process for preparing a fused ring compound having three boron atoms as claimed in claim 5, wherein the boronating agent is one or more of boron trifluoride, boron trichloride, boron triiodide and boron tribromide; the organic solvent is one or more of toluene, xylene, chlorobenzene, o-dichlorobenzene and 1,2, 4-trichlorobenzene.
7. A method of preparing a fused ring compound containing three boron atoms as claimed in claim 5, wherein the protective atmosphere comprises nitrogen and/or an inert gas.
8. A process for the preparation of fused ring compounds containing three boron atoms as claimed in claim 5, wherein the temperature of the reaction is 90-180 ℃ and the time of the reaction is 20-30 hours.
9. A method of claim 5, wherein a base is added under the above reaction conditions, and the base comprises one or more of N, N-diisopropylethylamine, triethylamine, 2,6, 6-tetramethylpiperidine, pentamethylpiperidine, 2, 6-dimethylpyridine, and N, N-dimethyl-p-toluidine.
10. 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; wherein the light-emitting layer comprises the fused ring compound having three boron atoms according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210145745.1A CN114426558B (en) | 2022-02-17 | Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210145745.1A CN114426558B (en) | 2022-02-17 | Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426558A true CN114426558A (en) | 2022-05-03 |
| CN114426558B CN114426558B (en) | 2024-05-31 |
Family
ID=
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 |
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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2665342B1 (en) | Composition for organic electroluminescent element, organic electroluminescent element, display device, and illuminator | |
| CN112592362A (en) | Condensed ring compound containing boron, nitrogen and sulfur atoms and five-membered aromatic heterocycle and organic electroluminescent device | |
| CN112645968B (en) | Fused ring compound containing two boron atoms and two oxygen family atoms and organic electroluminescent device | |
| TW201134823A (en) | Materials for electronic devices | |
| TW202212326A (en) | Compounds having spirobifluorene structures | |
| CN112851700A (en) | Condensed ring compound containing boron atom, oxygen atom and five-membered aromatic heterocycle and organic electroluminescent device | |
| CN112739795A (en) | Compounds useful as active compounds in organic electronic devices | |
| CN112480057B (en) | Oxacyclo compound, use thereof, and electronic device using the same | |
| CN112940048A (en) | Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device | |
| CN112979715A (en) | Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device | |
| CN113004340A (en) | Metal complex, organic electroluminescent material and organic electroluminescent element comprising the same | |
| CN113004339A (en) | Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device | |
| CN112930343A (en) | Material for organic electroluminescent device | |
| CN110483574B (en) | Fluorene spirophenyl tricarbazole derivative, preparation method and application thereof, and electronic device | |
| CN114181239B (en) | Boron-doped or phosphorus-doped fused ring compound containing naphthalene ring, preparation method thereof and light-emitting device | |
| CN112645969B (en) | Condensed ring compound containing boron, selenium/tellurium and nitrogen atoms and organic electroluminescent device | |
| CN114426558B (en) | Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device | |
| CN114426558A (en) | Fused ring compound containing three boron atoms, preparation method thereof and electroluminescent device | |
| CN112225686B (en) | Organic compound and electroluminescent device using the same | |
| Zhang et al. | Highly efficient through-space charge transfer TADF molecule employed in TADF-and TADF-sensitized organic light-emitting diodes | |
| CN113683646A (en) | Monocarbon borane-containing metal platinum complex and preparation method and application thereof | |
| CN109942635B (en) | Phenyl tricarbazole spiro derivative, preparation method and application thereof, and electronic device | |
| CN114456202B (en) | Fused ring compound containing four boron atoms, preparation method thereof and electroluminescent device | |
| CN115244060A (en) | Material for organic electroluminescent device | |
| CN114195809B (en) | Boron-doped or phosphorus-doped fused ring compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |